Electroconductive composition

ABSTRACT

A composition comprising a matrix of a thermoplastic, thermosetting or a structurally crosslinked polymer, in which is incorporated an electroconductive network of crystal needles of a charge transfer complex (abbreviated to CT complex) from an electron donor and an electron acceptor, characterized in that: 
     (1) the matrix contains uniformly distributed an excess, with respect to the CT complex formation, either of at least one electron donor or at least one electron acceptor as weakly polymer-soluble finely divided particles, 
     (2) the CT complex is formed either by at least one weakly polymer-soluble electron donor and at least one polymer-soluble electron acceptor or by at least one weakly polymer-soluble electron acceptor and at least one polymer-soluble electron donor, and 
     (3) microcrystalline needles grow from the weakly polymer-soluble particles in the polymer mass, which microcrystalline needles are in contact with and connect the weakly polymer-soluble particles to form a network which penetrates the polymer mass.

The present invention relates to an electroconductive compositioncomprising a polymer matrix and an electroconductive network, formed inthe matrix, of charge transfer (CT) complex from an electron donor andan electron acceptor, a method of producing said composition and the usethereof.

EP-A-0 285 564 describes substrates with electroconductive polymerlayers, which layers contain in the polymer matrix a network of radicalcation salts from tetrathio-, tetraseleno- or tetratellurotetracene andmetal salts or halogens. EP-A-0 362 141 discloses substrates which aredirectly coated with networks of such radical cation salts. EP-A-0 362142 describes substrates in which these networks are embedded in halogencontaining polymers. EP-A-0 362 143 describes substrates in which thesenetworks are embedded in halogen containing and photosensitive polymers.One disadvantage of these polymer layers is, that organic solutions mustbe used for their preparation. Another disadvantage of these layers isthat the electroconducting network is formed from CT complexes havingneedle-like crystals, which are relatively long and big, so that theamount of CT complexes can not be lowered too much without losingelectroconductivity.

It has now been found, surprisingly, that an electroconductivepercolated network system of a CT complex is formed in a polymer matrixby a solvent-free in situ process using an electron donor and anelectron acceptor, either the electron donor or the electron acceptorparticles being weakly soluble in the polymer matrix. Surprisingly theweakly polymer-soluble particles act as nucleating agents and amicrocrystalline polymer-penetrating network is formed. The polymercompositions show antistatic properties or electroconductivity. It wasfurther found that the size of the crystal-needles and thus theelectroconductivity or antistatic properties can be influenced by thesize of the weakly-polymer-soluble electron donor or acceptor.

One object of the instant invention is a composition comprising a matrixof a thermoplastic, thermosetting or a structurally crosslinked polymer,in which is incorporated an electroconductive network of crystal needlesof a charge transfer complex (abbreviated CT complex) of an electrondonor and an electron acceptor, characterized in that

(1) the matrix contains uniformly distributed an excess, with respect tothe CT complex formation, either of at least one electron donor or atleast one electron acceptor as weakly polymer-soluble finely devidedparticles,

(2) the CT complex is formed either by at least one weaklypolymer-soluble electron donor and at least one polymer-soluble electronacceptor or by at least one weakly polymer-soluble electron acceptor andat least one polymer-soluble electron donor, and

(3) the crystal needles growing from the weakly polymer-solubleparticles are formed in the polymer mass as microcrystalline needles,which are in contact and connect the weakly polymer-soluble particles,thus forming a network which penetrates the polymer mass.

Within the scope of the present invention the term "weaklypolymer-soluble" means that seed particles are being dissolved slowly sothat crystal growth is maintained only at the seed surface.

Preferably, the diameter of these particles is from 10 nm to 20 μm, morepreferably 20 nm to 20 μm, and most preferably 50 nm to 5 μm.

The crystals of CT complex are contained in the polymer matrix in anamount of preferably 10⁻³ to 2% by weight, more preferably 10⁻² to 1% byweight based on the polymer.

If S_(CT) denotes the solubility of the CT complex in the polymer (inMol/Kg) and if it is assumed that the molecular weight of the weaklypolymer-soluble donor or acceptor is about one half of the molecularweight of the corresponding CT complex, the loading of the polymer withthe weakly polymer-soluble donor or acceptor, X^(P) _(D) or X^(P) _(A)(in Mol/Kg), should be:

    X.sup.P.sub.D or X.sup.P.sub.A ≧2×S.sub.CT ×100  Mol/Kg!.

The factor of 100 ensures complete crystallization of the CT complex.

The above crystals have a length of preferably 0.1 μm to 1000 μm, morepreferably 1 μm to 500 μm, and most preferably 10 μm to 400 μm, and anaspect ratio (length:width ratio) of preferably 1 to 10000, morepreferably 10 to 5000 and most preferably 10 to 1000.

In the present invention, the network system incorporated in the polymermatrix comprises (a) particles of a weakly polymer-soluble electrondonor and CT-crystals grown from said particles, or comprises (b)particles of a weakly polymer-soluble electron acceptor and CT-crystalsgrown from said particles. These particles act, therefore, as nuclei forthe growth of the crystals as well as connecting points for theelectroconductive network system.

The solubility of a particular electron donor or acceptor is dependenton the polymer, so that the same electron donor and/or acceptor can besoluble in a particular polymer while they are weakly polymer-soluble inother polymers. Accordingly, it is necessary that a polymer for thematrix is chosen such that the above requirement (a) or (b) issatisfied. The solubility can easily be determined by simple tests, suchas by microscopic observation.

Illustrative examples of electron donors which can be weaklypolymer-soluble as well as polymer-soluble are the following compounds(see for example EP-A-0 285 564 and EP-A-0 023 988).

1. Compounds of formula I or Ia or mixtures thereof ##STR1## wherein X₁is S, Se or Te, R₁, R₂, R₃ and R₄ are each independently of one anotherH or Cl, or R₁ and R₂ as well as R₃ and R₄ are each ##STR2## or

R₁, R₂, R₃ and R₄ are each independent of one another phenylthio,4-methyl- or 4-methoxyphenylthio or 4-pyridylthio, R₅, R₆, R₇ and R₈ areeach independently of one another H or F, R₅ is CH₃ and R₆, R₇ and R₈are H or R₅, R₆, R₇ and R₈ are CH₃, R₅ and R₆ are CH₃ or Cl and R₇ andR₈ are H or R₅ and R₆ are H, R₇ is --COR₉ and R₈ is H or --COR₉, or R₅and R₆ are H and R₇ and R₈ together are --CO--O--CO or --CO--NR₁₀--CO--, R₉ is halogen, --OH, --NH₂, or the residue of an alcohol or ofprimary or secondary amine, or --OM, M being a cation and R₁₀ are H orthe residue of a primary amine which is diminished by NH₂ -- group.

In formulae I and Ia, X₁ is preferably S or Se. R₉ as halogen isespecially Cl.

M in the residue --OM can be a metallic or ammonium cation. As metalliccations those of alkali metals and alkaline earth metals, such asLi.sup.⊕, Na.sup.⊕, K.sup.⊕, Mg²⊕, Ca²⊕, Sr²⊕ and Ba²⊕ are preferred.Further, Zn²⊕ and Cd²⊕ are also suitable. As ammonium cations, NH⁴⊕ andprimary, secondary, tertiary or quaternary amines, which may containpreferably C₁ -C₁₂ alkyl, cyclohexyl, cyclopentyl, phenyl or benzylgroups, are preferred. The ammonium cations may be derived from 5- or6-membered heterocyclic amines, such as piperidine, pyrrole andmorpholine.

R₉ as a residue of an alcohol is preferably C₁ -C₆ -alkoxy or C₂ -C₆-hydroxyalkoxy, benzyloxy, phenoxy, cyclopentyloxy or cyclohexyloxy.

R₉ as a residue of a primary or secondary amine is derived preferablyfrom alkylamines with one or two C₁ -C₆ -alkyl groups. R₁₀ is preferablyH, C₁ -C₁₈ -alkyl, phenyl or benzyl.

R₁₀ as alkyl contains preferably 1 to 12, especially 1 to 6, carbonatoms. Examples of the alkyl, which may be linear or branched, aremethyl, ethyl, n- or i-propyl, n-, i- or t-butyl, pentyl, hexyl,2-ethylhexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl. Examplesof the alkoxy and hydroxyalkoxy are methoxy, ethoxy, propoxy, butoxy,pentoxy, hexoxy, β-hydroxyethoxy, γ-hydroxypropoxy, δ-hydroxybutoxy andω-hydroxyhexyloxy.

Especially preferred compounds represented by formulae I and Ia are5,6,11,12-tetrathiotetracene, 5,6,11,12-tetraselenotetracene, 2-fluoro-or 2,3-difluoro-5,6,11,12-tetraselenotetracene,2,3,8,9-tetramethyl-5,6,11,12-tetrathiotetracene,2,3,8,9-tetramethyl-5,6,11,12-tetraselenotetracene,2-methyl-5,6,11,12-tetrathiotetracene,2,3,8,9-tetrafluoro-5,6,11,12-tetrathiotetracene,2,3,8,9-tetrafluoro-5,6,11,12-tetraselenotetracene,2,3-dichloro-5,6,11,12-tetraselenotetracene,2-fluoro-5,6,11,12-tetratellurotetracene,2,3,6,7-tetrathiophenyl-1,4,5,8-tetrathionaphthalene,2,3,6,7-tetramethoxyphenyl-1,4,5,8-tetrathionaphthalene,2,3,6,7-tetra-4-pyridylthio-1,4,5,8-tetrathionaphthalene,2,3,6,7-tetraphenylthio-1,4,5,8-tetraselenonaphthalene, and thecompounds ##STR3##

2. Compounds represented by formula II ##STR4## wherein R₁₁, R₁₂, R₁₃and R₁₄ are each independently of one another C₁ -C₁₂ -alkyl, phenyl, C₁-C₁₂ -alkylphenyl, C₁ -C₁₂ -alkoxyphenyl or especially H, or R₁₁, andR₁₂ together sare a residue of ##STR5## --(CH₂)_(p) --, --C(CH₃)₂--(CH₂)_(p) --C(CH₃)₂ -- or --S--(CH₂)_(p) --S--, p is an integer 1-12and R₁₃ and R₁₄ are each independently of the other C₁ -C₁₂ -alkyl,phenyl, C₁ -C₁₂ -alkylphenyl, C₁ -C₁₂ -alkoxyphenyl or especially H, orR₁₁, and R₁₂ are each independently of the other C₁ -C₁₂ -alkyl, phenyl,C₁ -C₁₂ -alkylphenyl,

C₁ -C₁₂ -alkoxyphenyl or especially H and R₁₃ and R₁₄ together are aresidue of ##STR6## --(CH₂)_(p) --, --C(CH₃)₂ --(CH₂)_(p) --C(CH₃)₂ --or --S--(CH₂)_(p) --S--, p is an integer 1-12, and X₂, X₃, X₄ and X₅stand for Se or especially S.

3. Diheterodipyranes and their derivatives of formula III ##STR7##wherein X₆ is for S, Se or N--C₁ -C₁₂ -alkyl and R₁₅ is H, C₁ -C₁₂-alkyl or substituted or unsubstituted phenyl. X₆ is preferably S, Se orN--C₁ -C₁₂ -alkyl, and R₁₅ is preferably H, C₁ -C₆ -alkyl or phenyl.

The above compounds of 1-3 are well known in the art. The compounds of 1represented by general formulae I and Ia are described in detail forexample in EP-A-0 285 564. The compounds of 2 and 3 represented bygeneral formulae II and III are described for example in EP-A-0 023 988.The compounds 1-3 can be used alone or a mixture of at least two ofthem.

Examples of electron acceptors which can be polymer-soluble as well asweakly polymer-soluble are the following compounds (see for exampleEP-A-0 285 564, EP-A-0 362 142, EP-A-0 523 003 and DE-36 19 606).

1. Halogen containing organic compounds which cleave halogen (byapplying energy, if necessary) and form CT complexes with electrondonors. The energy can be for example thermal energy or radiationenergy. If the energy is radiation energy, irradiation can be carriedout non-imagewise or imagewise using a mask or by means of imagewisecontrol of the radiation. Thermal energy means for example a temperatureof from room temperature to 350° C., especially from 50° C. to 200° C.The halogen-containing organic compounds contain preferably Cl-, Br- orI-residues, and are halogenated, saturated or unsaturated, aliphatic,cycloaliphatic, aliphatic-heterocyclic, aromatic or heteroaromaticorganic compounds which may be substituted by --CN, HO--, ═O, C₁ -C₄-alkyl, C₁ -C₄ -alkoxy, --CO--C₁ -C₄ -alkyl or --COOC₁ -C₄ -alkyl. Thehalogen compounds may be used singly or as a mixture. The organiccompounds are preferably chlorinated and/or brominated. The compoundsmay be monohalogenated as for example N-brominated or N-chlorinateddicarboxylic acid imides. C-halogenated compounds preferably have ahigher degree of halogenation; preferably, they are at least 80%C-halogenated, especially C-brominated and/or C-chlorinated. Compoundswhose halogen atoms are activated by electron attracting groups areparticularly suitable.

Examples of halogenated organic compounds are tetrabromomethane,bromoform, trichlorobromomethane, hexachloropropane,hexachlorocyclopropane, hexachlorocyclopropene,hexachlorocyclopentadiene, hexachloroethane, N-chlorosuccinimide,octachloropropane, n-octachlorobutane, n-decachlorobutane,tetrabromoethane, hexabromoethane, tetrabromobenzoquinone,2,4,4,6-tetrabromo-2,5-cyclohexadienone, hexabromobenzene, chloranil,hexachloroacetone, 1,4,5,6,7,7-hexachloro-5-norbornen-2,3-dicarboxylicacid, 1,2,5,6,9,10-hexabromocyclododecane, tetrachloroethylene,perchlorocyclopentadiene, perchlorobutadiene,dichloroacetaldehyde-diethylacetal, 1,4-dichloro-2-butene,1,3-dichloro-2-butene, 3,4-dichloro-1-butene, tetrachlorocyclopropane,1,3-dichloroacetone, 2,3,5,6-hexachloro-p-xylene,1,4-bis(trichloromethyl)-benzene, 1,3-dibromopropane, 1,6-dibromohexane,3-chloropropionic acid ethyl ester, 3-chlorotoluene, 2-chloropropionicacid methyl ester, 2-chloroacrylonitrile, trichloroacetic acid ethylester, 1,2,3-trichloropropane, 1,1,2-trichloroethane, chloroformic acidbutyl ester, trichloroethylene, 2,3-dichloromaleic anhydride,1,12-dibromododecane, α,α'-dibromo-p-xylene, α,α'-dichloro-o-xylene,phenacyl chloride or bromide, 1,10-dibromododecane,α,α'-dichloro-p-xylene, α,α'-dibromo-m-xylene, iodoacetonitrile,2,3-dichloro-5,6-dicyanobenzoquinone, 2,3-dichloropropionic acid methylester, 1-bromo-2-chloroethane, 1-bromo-2-chloropropane, chloroformicacid-2-bromoethyl ester, iodoacetic acid ethyl ester, N-chloro-,N-bromo- or N-iodosuccinimide or -phthalimide, or mixtures of thesecompounds.

These halogen containing compounds are described in detail for examplein EP-A-0 285 564.

As other examples of the above halogen-containing organic compounds,there are also halogen containing polymers/monomers and prepolymers forthermosetting polymers and/or photopolymers. Preferredhalogen-containing polymers are for example thermoplastic polymerscontaining aliphatic or cycloaliphatic side groups, which side groupsare bound to the polymer backbone via a group --O--, --CO--,--CO--OA--OCO-- or --CO--O-- and contain at least one Cl-, Br- or I-atomin α-, β-, γ- or ω-position, wherein A is C₂ -C₁₂ -alkylene, C₄ -C₁₂-cycloalkylene, C₄ -C₁₂ -cycloalkylene-CH₂ --, C₄ -C₁₂-cycloalkylene-(CH₂)₂ --, benzylene or xylylene, which is unsubstitutedor substituted by OH, Cl, Br or phenyl.

The aliphatic side groups are for example linear or branched C₁ -C₁₂ -,especially C₁ -C₆ -, particularly C₁ -C₄ -alkyl. Examples are methyl,ethyl and the isomers of propyl, butyl, pentyl, hexyl, heptyl, octyl,nonyl, decyl, undecyl and dodecyl. Examples of cycloaliphatic groups areespecially cyclopentyl and cyclohexyl. Particularly preferred are methylor ethyl which are substituted by Cl, Br or I, particularly Cl, forexample --CH₂ Cl, --CHCl₂, --CCl₃, --CHClCH₃, --CCl₂ CH₃, --CHCl--CH₂Cl, --CCl₂ --CH₂ Cl, --CHCl--CHCl₂, --CCl₂ --CHCl₂, --CCl₂ --CCl₃, --CH₂--CH₂ Cl, --CH₂ --CHCl₂ or --CH₂ --CCl₃.

The groups --O, --O--CO--, --CO--, --OA--O--CO-- or --CO--O-- preferablyhave groups of the formula --C_(m) H_(n) Y_(o) bonded to them, wherein mis a number from 1 to 12, n is 0 or a number from 1 to 24, o is a numberfrom 1 to 25 and n+o=2 m+1, Y is Cl, Br or I and A is C₂ -C₁₂ -alkylene,C₄ -C₁₂ -cycloalkylene, C₄ -C₁₂ -cycloalkylene-CH₂ --, C₂ -C₁₂-cycloalkylene-(CH₂)₂ --, benzylene or xylylene which is unsubstitutedor substituted by OH, Cl, Br or phenyl, Y is preferably Cl, m ispreferably 1 to 6, especially 1 to 4, n is preferably 0 or 1 to 12,especially 1 to 8, o is preferably 1 to 13, especially 1 to 9, and n+o=2m+1.

The thermoplastic polymers can be based on different polymers containinghydroxy groups or caboxyl groups, or mixtures of said polymers, e.g.polyesters, polyester-amides, polyurethanes, polyamides, polycarbonatesand polyimides derived from monomers containing hydroxy groups,saponified and unsubstituted or hydroxyalkylated polymers of vinylesters or ethers, hydroxylated polydiolefins such as polybutadiene orpolyisoprene, polyacrylates or polymethacrylates containing hydroxyalkylradicals in the ester group, polyacrylic or polymethacrylic acids, orreduced polyketones or copolymers thereof, as well as copolymers ofunsubstituted or hydroxyalkyleted vinyl alcohol, acrylates ormethacrylates, acrylic acids or methacrylic acids or diolefins withcomonomers such as acrylonitrile, olefins, diolefins, vinyl chloride,vinylidene chloride, vinyl fluoride, vinylidene fluoride, styrene,α-methylstyrene, maleic anhydride, maleimide, vinyl ethers and vinylesters, and polyadducts of unsubstituted or hydroxyalkylated epoxycompounds containing an average of more than one epoxy group permolecule, and diols, primary monoamines, di-secondary diamines,di-secondary linear or cyclic dicarboxylic acid diamides or dicarboxylicacids.

In a preferred embodiment, the thermoplastic polymer is a linearpolyadduct of a glycidyl compound containing an average of more than oneepoxy group, and a diol, a primary monoamine, a di-secondary diamine, adi-secondary linear or cyclic dicarboxylic acid diamide or adicarboxylic acid, in which polyadduct the H atom of the secondary OHgroups is at least partially substituted by a group --CO--C_(m) H_(n)Y_(o), wherein m is a number from 1 to 12, n is 0 or a number from 1 to24, o is a number from 1 to 25 and n+o=2 m+1, and Y is Cl, Br or I.

The polyadducts are preferably based on glycidyl compounds containing anaverage of two epoxy groups per molecule.

Especially suitable glycidyl compounds are those containing two glycidylgroups, β-methylglycidyl groups or 2,3-epoxycyclopentyl groups bonded toa hetero atom (for example, sulfur or, preferably, oxygen or nitrogen),especially bis(2,3-epoxycyclopentyl)ether; diglycidyl ethers ofpolyhydric aliphatic alcohols such as 1,4-butanediol, or polyalkyleneglycols such as polypropylene glycol; diglycidyl ethers ofcycloaliphatic polyols such as 2,2-bis(4-hydroxycyclohexyl)propane;diglycidyl ethers of polyhydric phenols such as resorcinol,bis(p-hydroxyphenyl)methane,2,2-bis(p-hydroxyphenyl)propane(═diomethane),2,2-bis(4'-hydroxy-3,5'-dibromophenyl)propane and1,3-bis(p-hydroxyphenyl)ethane; di(β-methylolycidyl)ethers of thedihydric alcohols or dihydric phenols listed above; diglycidyl esters ofdicarboxylic acids such as phthalic acid, terephthalic acid, Δ⁴-tetrahydrophthalic acid and hexahydrophthalic acid; N,N-diglycidylderivatives of primary amines and amides and heterocyclic nitrogen basescontaining two nitrogen atoms, and N,N'-diglycidyl derivatives ofdi-secondary diamides and diamines, such as N,N-diglycidylaniline,N,N-diglycidyltoluidine, N,N-diglycidyl-p-aminophenyl methyl ether andN,N'-dimethyl-N,N'-diglycidyl-bis(p-aminophenyl)methane;N',N"-diglycidyl-N-phenyl isocyanurate; N,N'-diglycidylethyleneurea;N,N'-diglycidyl-5,5-dimethylhydantoin,N,N'-diglycidyl-5-isopropylhydantoin,N,N-methylene-bis(N',N-diglycidyl-5,5-dimethylhydantoin) and1,3-bis(N-glycidyl-5,5-dimethylhydantoin)-2-hydroxypropane; andN,N'-diglycidyl-5,5-dimethyl-6-isopropyl-5,6-dihydrouracil.

The glycidyl compounds can be reacted with aliphatic, cycloaliphatic oraromatic diols to give the preferred polyadducts, a secondary alcoholgroup, which can be esterified with carboxylic acids containing Cl, Brand/or I, being formed by addition to the glycidyl group.

However, the glycidyl compounds can also be reacted with the followingcompounds to give linear polyadducts by polyaddition: primary aliphatic,cycloaliphatic or aromatic monoamines (e.g. aniline, toluidine, C₁ -C₁₂-alkylamines, C₂ -C₁₂ -hydroxyalkylamines), aliphatic, cycloaliphatic oraromatic dicarboxylic acids (e.g. maleic acid, adipic acid,trimethyladipic acid, sebacic acid, azelaic acid, succinic acid,dodecylsuccinic acid, phthalic acid, terephthalic acid, Δ⁴-tetrahydrophthalic acid, hexahydrophthalic acid, Δ⁴-methylhexahydrophthalic acid, 3,6-endomethylene-Δ⁴ -tetrahydrophthalicacid, 4-methyl-3,6-endomethylene-Δ⁴ -tetrahydrophthalic acid) oraliphatic, cycloaliphatic, heterocyclic or aromatic bis-secondary aminesor bis-secondary carboxyamides (e.g. N,N'-dimethylethylenediamine,N,N'-dimethylpropylene-1,3-diamine, N,N'-dimethylhexamethylenediamine,N,N'-dicyclohexylhexamethylenediamine,N,N',N"-trimethyldiethylenetriamine, N,N'-diethylpropylene-1,3-diamine,N-methyl-3,5,5-trimethyl-3-(methylaminomethyl)cyclohexylamine,N,N'-dimethylated or N,N'-diethylated aromatic diamines, e.g. m- orp-phenylenediamine, bis(4-aminophenyl)methane orbis(4-aminophenyl)sulfone, 2,2-bis-(4-aminophenyl)propane,N,N-dimethyl-m-xylylenediamine, as well as ethyleneurea,5,5-dimethylhydantoin, 5-isopropylhydantoin,N,N-methylene-bis-5,5-dimethylhydantoin,1,3-bis(5,5-dimethylhydantoin)-2-hydroxypropane,5,5-dimethyl-6-isopropyl-5,6-dihydrouracil).

In a preferred embodiment, the polyadduct contains

a) 100 to 0.1 mol % of identical or different structural units offormula IV ##STR8## and b) 99.9 to 0 mol % of identical or differentstructural units of formula V ##STR9## based on the polyadduct, whereinA₁ and A₂ are each independently of the other the radical of a diolcontaining aliphatic or aromatic diol groups, from which two hydroxylgroups have been removed, A' is H, unsubstituted or OH-substituted C₁-C₂₀ -alkyl, C₁ -C₂₀ -acyl or aminocarbonyl N-substituted by a C₁ -C₂₀-hydrocarbon radical, --OA₃ -- is a direct bond or A₃ is ethylene whichis unsubstituted or substituted by C₁ -C₁₆ -alkyl.

The polyadduct preferably contains 100 to 20 and especially 30 to 100mol % of structural units of formula IV and 80 to 0 especially 70 to 0mol % of structural units of formula V.

In a preferred embodiment, A₁ and A₂ are identical radicals. A₁ and A₂as radical having aliphatic diol groups preferably contain 2 to 12 andespecially 2 to 8 C atoms. The hydroxy groups can be bonded toopen-chain or cyclic aliphatic radicals. Examples of typical aliphaticradicals are linear or branched C₂ -C₁₂ -alkylene, C₃ -C₈-cycloalkylene, C₁ -C₄ -alkyl-C₅ -C₈ -cycloalkyl, cyclohexylmethylene orcyclohexyldimethylene. Examples are ethylene, 1,2- or 1,3-propylene,1,2-, 1,3- or 1,4-butylene, 1,2-, 1,3-, 1,4- or 1,5-pentylene, 1,2-,1,3-, 1,4-, 1,5- or 1,6-hexylene, heptylene, octylene, nonylene,decylene, undecylene, dodecylene, 1,3-cyclopentylene, 1,3- or1,4-cyclohexylene, 2-methyl-1,4-cyclohexylene andcyclohexyl-1,4-dimethylene.

The aromatic diol groups of the diols used for the polyadducts areespecially phenolic groups. The diol radicals having phenolic groupspreferably contain 6-30 and especially 6-20 C atoms. A preferredembodiment consists of polyadducts in which A₁ and A₂ are independentlyof the other a radical of the formula ##STR10## wherein Y₁ is a directbond, C₁ -C₄ -alkylene, C₂ -C₁₂ -alkylidene, C₅ -C₈ -cycloalkylidene,--O--, --S--, --SO--, --SO₂ --, --CO--, --CO₂ --, --N(C₁ -C₄ -alkyl)- or--Si(CH₃)₂ --, A₄ and A₅ are independently of the other H, halogen, C₁-C₄ -alkyl or C₁ -C₄ -alkoxy, x is 0, 1 or 2 and y is 0 or 1.

Y₁ is preferably a direct bond, methylene, ethylene, C₂ -C₆ -alkylidene,cyclohexylidene, cyclopentylidene, --O-- or --S--. A₄ and A₅ arepreferably H or methyl and y is preferably 1.

A₁ and A₂ are especially the radical ##STR11##

A₃ as alkyl-substituted ethylene preferably contains C₁ -C₄ -alkyl andespecially C₁ or C₂ alkyl. Ethylene, 1,2-propylene and 1,2- or2,3-butylene are especially preferred.

A' as C₁ -C₂₀ -alkyl can be linear or branched. A' as acyl can be e.g.C₁ -C₂₀ -alkyl-CO--, C₅ -C₈ -cycloalkyl-CO--, C₁ -C₁₅ -alkyl-C₅ -C₈-cycloalkyl-CO--, C₅ -C₈ -cycloalkyl-CH₂ --CO--, C₁ -C₁₄ -alkyl-C₅ -C₈-cycloalkyl-CH₂ --CO--, phenyl-CO--, benzyl-CO--, C₁ -C₁₄-alkyl-phenyl-CO-- or C₁ -C₄ -alkyl-benzyl-CO--. The hydrocarbon radicalin the aminocarbonyl can be e.g. C₁ -C₂₀ -alkyl-, C₅ -C₈ -cycloalkyl-,C₁ -C₁₅ -alkyl-C₅ -C₈ -cycloalkyl, C₅ -C₈ -cycloalkyl-CH₂ --, C₁ -C₄-alkyl-C₅ -C₈ -cycloalkyl-CH₂ --, phenyl-, benzyl-, C₁ -C₁₄-alkyl-phenyl- or C₁ -C₁₄ -alkyl-benzyl-. A' is preferably H.

In another preferred embodiment, the thermoplastic polymer is ahomopolymer or a copolymer of an acrylic acid ester or methacrylic acidester containing chlorinated, brominated and/or iodinated aliphatic orcycloaliphatic groups in the ester group.

In an especially preferred embodiment, the polymer contains

a) 0.1 to 100 mol % of at least one structural unit of formula VI##STR12## and b) 0 to 99.9 mol % of at least one structural unit offormula VII ##STR13## based on the polymer, wherein A₆ is H or methyl;A₇ is a radical --(A--O--CO)_(z) --C_(m) H_(n) Y_(o), wherein z is 0 or1, m is a number from 1 to 12, n is 0 or a number from 1 to 24, o is anumber from 1 to 25 and n+o=2 m+1, Y is Cl, Br or I and A is C₂ -C₁₂-alkylene, C₄ -C₁₂ -cycloalkylene, C₄ -C₁₂ -cycloalkylene-CH₂ --, C₂-C₁₂ -cycloalkylene-(CH₂)₂ --, benzylene or xylylene which isunsubstituted or substituted by OH, Cl, Br or phenyl; A₈ is H, C₁ -C₆-alkyl or --COOA₁₁ ; A₉ is H, F, Cl, CN or C₁ -C₆ -alkyl; and A₁₀ is H,F, Cl, CN, A₁₁ --O--, C₁ -C₁₂ -alkyl, --COOA₁₁, --O--CO--A₁₁,--COOA--OH, ##STR14## or phenyl, wherein A is as defined above and A₁₁is C₁ -C₁₈ -alkyl, C₅ -C₇ -cycloalkyl, (C₁ -C₁₂ -alkyl)-C₅ -C₇-cycloalkyl, phenyl, (C₁ -C₁₂ -alkyl)phenyl, benzyl or (C₁ -C₁₂-alkyl)benzyl.

The polymer preferably contains 100 to 20 and especially 100 to 30 mol %of structural units of formula VI and 80 to 0 and especially 70 to 0 mol% of structural units of formula VII.

A₆ is preferably methyl, Y, m, n and o have the preferred meanings givenabove and z is preferably 1.

A is preferably unsubstituted or substituted by OH or Cl. A as alkylenepreferably contains 2 to 6 C atoms. The alkylene can be linear orbranched. Examples are ethylene and the isomers of propylene, butylene,pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecyleneand dodecylene. A as cycloalkylene is especially cyclohexylene and, inthe radicals containing cycloalkylene, is preferably cyclohexylene.

A₁₁, can be linear or branched C₁ -C₁₈ -, preferably C₁ -C₁₂ - andespecially C₁ -C₆ -alkyl. A₁₁ as cycloalkyl is especially cyclopentyl orcyclohexyl. When A₁₁ is (C₁ -C₁₂ -alkyl)cycloalkyl, the cycloalkyl isespecially cyclopentyl or cyclohexyl and the alkyl group can be linearor branched and preferably contains 1 to 6 and especially 1 to 4 Catoms. When A₁₁ is alkylphenyl or alkylbenzyl, the alkyl group can belinear or branched and preferably contains 1 to 6 and especially 1 to 4C atoms.

A₈ is preferably H. A₈ as alkyl is preferably methyl or ethyl. When A₈is --COOA₁₁, A₁₁ is preferably C₁ -C₁₂ - and especially C₁ -C₆ -alkyl.

A₉ as alkyl is preferably C₁ -C₄ -alkyl, e.g. methyl, ethyl, n-propyl orn-butyl. A₉ is preferably H, Cl or C₁ -C₄ -alkyl.

When A₁₀ is the group A₁₁ --O--, A₁₁ is preferably C₁ -C₁₂ - andespecially C₁ -C₆ -alkyl. A₁₀ as alkyl preferably contains 1 to 6 andespecially 1 to 4 C atoms. When A₁₀ is the group --COOA₁₁, A₁₁ ispreferably C₁ -C₁₂ - and especially C₁ -C₆ -alkyl, cyclopentyl orcyclohexyl. When A₁₀ is the group --OCO--A₁₁, A₁₁, is preferably C₁-C₁₂ - and especially C₁ -C₆ -alkyl, phenyl or benzyl.

When A₁₀ is the group --COOAOH, A has the preferred meanings givenabove.

In a preferred embodiment, A₈ is H, A₉ is H, F, Cl, methyl or ethyl andA₁₀ is F, Cl, CN, C₁ -C₄ -alkyl, C₁ -C₆ -alkoxy, --COO--C₁ -C₆ -alkyl,--COO--A--OH, --OOC--C₁ -C₆ -alkyl or phenyl.

In a preferred polyadduct, A₆, is methyl; A₇ is a radical--A--O--CO--C_(m) H_(n) Y_(o), wherein m is a number from 1 to 6, n is 0or a number from 1 to 12, o is a number from 1 to 13 and n+o=2 m+1, Y isCl and A is C₂ -C₆ -alkylene, cyclopentylene, cyclohexylene,cyclopentylene-CH₂ --, cyclohexylene-CH₂ -- or cyclohexylene-(CH₂)₂ --which is unsubstituted or substituted by OH or Cl; A₈ is H; A₉ is H, F,Cl or C₁ -C₄ -alkyl; and A₁₀ is H, F, Cl, CN, A₁₁ --O--, C₁ -C₆ -alkyl,--COOA₁₁, --O--CO--A₁₁, --COOA--OH, ##STR15## or phenyl, A being asdefined above and A₁₁ being C₁ -C₆ -alkyl, C₅ - or C₆ -cycloalkyl,phenyl or benzyl.

In another preferred polyadduct, A₆ is methyl; A₇ is a radical--A--O--CO--C_(m) H_(n) Y_(o), wherein m is a number from 1 to 4, n is a0 or a number from 1 to 8, o is a number from 1 to 13 and n+o=2 m+1, Yis Cl and A is a linear C₂ -C₆ -alkylene or --CH₂ CHOHCH₂ --; A₈ and A₉are H; and A₁₀ is C₁ -C₆ -alkyl.

Especially preferred polyadducts are those in which, in formula VI, A₆is H or CH₃ and A is linear or branched C₂ -C₆ -alkylene, cyclopentyleneor cyclohexylene, and in formula VII, A₈ is H, A₉ is H or methyl and A₁₀is --COOA₁₁ or --COOAOH, A and A₁₁ being defined above, including thepreferred meanings.

In another preferred embodiment, the thermoplastic polymer is ahomopolymer or copolymer of vinyl alcohol in which the H atom of thesecondary OH group is at least partially substituted by a group--Z--C_(m) H_(n) Y_(o), wherein Z is a direct bond, --CO-- or --A₃--O--CO--, Y is Cl, Br or I, m is a number from 1 to 12, n is 0 or anumber from 1 to 24, o is a number from 1 to 25 and n+o=2 m+1, A₃ beingethylene which is unsubstituted or substituted by C₁ -C₆ -alkyl.

Preferred polyadducts are those containing

a) 90 to 0.1 mol % of structural units of formula VIII ##STR16## and b)99.9 to 10 mol % of identical or different structural units of formulaIX ##STR17## wherein Z is a direct bond, --CO-- or --A₃ --O--CO--, A₃being ethylene which is unsubstituted or substituted by C₁ -C₁₆ -alkyl;Y is Cl, Br or I; m is a number from 1 to 12, n is 0 or a number from 1to 24, o is a number from 1 to 25 and n+o=2 m+1; A₁₂ is H, C₁ -C₆ -alkylor --COOA₁₁ ; A₉ is H, F, Cl, CN or C₁ -C₆ -alkyl; and A₁₂ is H, F, Cl,CN, OH, A₁₁ O--, C₁ -C₁₂ -alkyl, --COOA₁₁, --O--CO--A₁₁, --OAOH orphenyl, A₁₁ being C₁ -C₁ C₁₈ -alkyl, C₅ -C₇ -cycloalkyl, (C₁ -C₁₂-alkyl)-C₅ -C₇ -cycloalkyl, phenyl, (C₁ -C₁₂ -alkyl) phenyl, benzyl or(C₁ -C₁₂ -alkyl)benzyl and A being ethylene which is unsubstituted orsubstituted by C₁ -C₁₆ -alkyl.

The adduct preferably contains 70 to 10 and especially 60 to 20 mol % ofstructural units of formula VIII and 30 to 90 and especially 40 to 80mol % of structural units of formula IX.

A₈ and A₉ in formula IX have the preferred meanings given above. A andA₁₁ also have the preferred meanings given above.

A₁₂ is preferably H, F, Cl, CN, OH, A₁₁, --O--, C₁ -C₄ -alkyl, --COOA₁₁,--O--CO--A₁₁, phenyl, --OCH₂ CH₂ OH or --OCH₂ CH(CH₃)OH, A₁₁ being C₁-C₆ -alkyl.

Especially preferred polyadducts are those in which A₈ and A₉ are H andA₁₂ is --OCOA₁₁, wherein A₁₁ is C₁ -C₁₈ -alkyl, C₅ -C₇ -cycloalkyl, (C₁-C₁₂ -alkyl)-C₅ -C₇ -cycloalkyl, phenyl, benzyl, (C₁ -C₁₂ -alkyl)phenylor (C₁ -C₁₂ -alkyl)benzyl.

In a preferred embodiment, Z is a direct bond, --CO--, --CH₂ CH₂ O--CO--or --CH₂ CH(CH₃)O--CO--; Y is Cl; m is a number from 1 to 6, n is 0 or anumber from 1 to 12, o is a number from 1 to 13 and n+o=2 m+1; A₈ and A₉are H; and A₁₂ is H, F, Cl, CN, OH, A₁₁ O--, C₁ -C₄ -alkyl, --COOA₁₁,--O--CO--A₁₁, phenyl, --OCH₂ CH₂ OH or --OCH₂ CH(CH₃)OH, A₁₁, being C₁-C₆ -alkyl, C₅ - or C₆ -cycloalkyl, phenyl or benzyl.

These halogen containing polymers are described in detail for example inEP-A-0 362 142. Preferred halogen containing monomers are those used forthe preparation of the above halogen containing polymers, and preferredprepolymers are for example derived from these halogen containingmonomers.

The halogen containing organic compound may also be the polymer matrixitself. Examples of such halogen containing matrix polymers arepolychloroprene, chlorinated rubber, chlorinated or chlorosulfonatedpolyethylene, epichlorohydrin homopolymers and copolymers, especiallypolymers of halogen containing vinyl compounds, such as polyvinylchloride, polyvinylidene chloride, polyvinyl fluoride or polyvinylidenefluoride, and copolymers thereof such as vinyl chloride/vinylidenechloride, vinyl chloride/vinyl acetate or vinylidene chloride/vinylacetate.

2. Salts of oxidatively acting cations with non-nucleophilic anions.Examples of such anions are halogen (F.sup.⊖, Cl.sup.⊖), BF₄.sup.⊖,SbF₆.sup.⊖, AsF₆.sup.⊖ and PF₆.sup.⊖, and examples of the cations arethose of transition metals or rare earth metals, such as Fe(III),Co(III) and Ce(IV), or non-metallic cations such as NO.sup.⊕. Examplesof the salts are NOBF₄, FeCl₃ and Co(PF₆)₃. These compounds aredescribed for example in EP-A-0 285 564.

3. CuCl₂ and CuBr₂, and their aquo-, solvent- or ammonium complexes.Solvent complexes of CuCl₂ and CuBr₂ with polar aprotic or polar proticsolvents are well known in the art. Monomer, dimer as well as polymercomplexes can be used. Preferable solvents which form complexes withCuCl₂ and CuBr₂, are those having heteroatoms such as for exampleoxygen, sulfur, phosphor and nitrogen. Examples of such solvents areethers (diethyl ether, dibutyl ether, ethylene glycol dimethyl ordiethyl ether), esters and lactones (ethyl acetate, γ-butyrolactone),sulfones (dimethyl sulfone, tetramethylene sulfone) and amines(pyridine, α-pyridone, α-methylpyridine, ethylenediamine,N,N'-dimethylethylenediamine, 1-(β-aminoethyl)pyridine). CuCl₂ and itsaquo and solvent complexes are described for example in EP-A-0 523 003.Suitable ammonium complexes are for example tetramethylammonium-,tetraethylammonium-, tetrapropylammonium-, tatrabutylammonium-,tetrapentylammonium-, tetrahexylammonium-, tetraheptylammonium- andtetraoctylammonium-CuCl₂, and -CuBr₂. These complexes can readily beprepared in a manner known per se.

4. Tetracyanoethylene, tetracyanoquinodimethanes of formula X orN,N'-dicyanoquinodimethanes of formula XI, as well as mixtures ofcompounds represented by formula X and/or XI ##STR18## wherein R₁₆, R₁₇,R₁₈ and R₁₉ are each independently of one another C₁ -C₁₂ -alkyl, C₁-C₁₂ -alkoxy, C₁ -C₁₂ -alkylsulfido, phenyl, halogen, --CN or especiallyH, R₁₆ and R₁₇ are together a residue of ##STR19## --(CH₂)_(m) --,--(CH₂)_(m) --O--(CH₂)_(m) -- or --O--(CH₂)_(m) --O--, m is an integer1-12 and R₁₈ and R₁₉ are each independently of the other C₁ -C₁₂ -alkyl,C₁ -C₁₂ -alkoxy, C₁ -C₁₂ -alkylsulfido, phenyl, halogen, --CN orespecially H, or R₁₆ and R₁₇ are each independently of the other C₁ -C₁₂-alkyl, C₁ -C₁₂ -alkoxy, C₁ -C₁₂ -alkylsulfido, phenyl, halogen, --CN orespecially H and R₁₈ and R₁₉ are together a residue of ##STR20##--(CH₂)_(m) --, --(CH₂)_(m) --O--(CH₂)_(m) -- or --O--(CH₂)_(m) --O--, mis an integer 1-12, in which the condensed aromatic rings may besubstituted by one or two chlorine or bromine atoms or C₁ -C₄ -alkoxyand/or C₁ -C₄ -alkyl groups.

5. Metal complexes of formula XII ##STR21## wherein Me means Pt or Pd,and R₂₀ is --CN, --CH₃ or --CF₃.

The compounds represented by formula X, XI and XII are described forexample in DE 36 19606.1

6. Quinones such as benzoquinone, naphthoquinone and anthraquinone,which may be unsubstituted or substituted by C₁ -C₁₂ -alkyl, C₁ -C₁₂-alkoxy, C₅ -C₇ -cycloalkyl, halogen, benzyl, phenyl, naphthyl, --CF₃,--CN, or --NO₂, as well as mixtures among them. These quinones are wellknown in the art.

The above mentioned electron acceptors may be used alone or as a mixtureof at least two of them.

The CT-crystal forming the electroconductive network of the instantinvention is represented by general formula XIII

    (D)(A).sub.n                                               (XIII),

wherein D is an electron donor, A is an electron acceptor and n is anumber 0.1-2.0, preferably 0.3-0.9 and most preferably 0.3-0.8, and theelectron donor is weakly polymer-soluble if the electron acceptor ispolymer-soluble while the electron donor is polymer-soluble if theelectron acceptor is weakly polymer-soluble.

Preferably, the electron donor D is a compound represented by formula Ior Ia, especially 5,6,11,12-tetrathiotetracene,5,6,11,12-tetraselenotetracene, 2-fluoro- or2,3-difluoro-5,6,11,12-tetraselenotetracene,2,3,8,9-tetramethyl-5,6,11,12-tetrathiotetracene,2,3,8,9-tetramethyl-5,6,11,12-tetraselenotetracene,2-methyl-5,6,11,12-tetrathiotetracene,2,3,8,9-tetrafluoro-5,6,11,12-tetrathiotetracene,2,3,8,9-tetrafluoro-5,6,11,12-tetraselenotetracene,2,3-dichloro-5,6,11,12-tetraselenotetracene,2-fluoro-5,6,11,12-tetratellurotetracene,2,3,6,7-tetrathiophenyl-1,4,5,8-tetrathionaphthalene,2,3,6,7-tetramethoxyphenyl-1,4,5,8-tetrathionaphthalene,2,3,6,7-tetra-4-pyridylthio-1,4,5,8-tetrathionaphthalene,2,3,6,7-tetraphenylthio-1,4,5,8-tetraselenonaphthalene, or the compound##STR22##

The most preferred electron donor is 5,6,11,12-tetrathiotetracene or5,6,11,12-tetraselenotetracene.

Preferred electron acceptor A is one selected from the group consistingof the above described halogen containing organic compounds includinghalogen containing polymers, monomers and prepolymers and halogencontaining matrix polymers, CuCl₂ and CuBr₂ and their aquo, solvent andammonium complexes. Most preferred is anhydrous CuCl₂, anhydrous CuBr₂,an ammonium complex of CuCl₂ or an ammonium complex of CuBr₂.

Illustrative examples of themoplastic polymers suitable as matrixpolymers are the following (see for example EP-A-0 523 003):

1. Polymers of monoolefins and diolefins, for example polypropylene,polyisobutylene, polybut-1-ene, polymethylpent-1-ene, polyisoprene orpolybutadiene, as well as polymers of cycloolefins, for example ofcyclopentene or norbornene, polyethylene (which can be uncrosslinked orcrosslinked), for example high density polyethylene (HDPE), low densitypolyethylene (LDPE), linear low density polyethylene (LLDPE), branchedlow density polyethylene (BLDPE).

2. Mixtures of the polymers mentioned under 1), for example mixtures ofpolypropylene with polyisobutylene, polypropylene with polyethylene (forexample PP/HDPE, PP/LDPE) and mixtures of different types ofpolyethylene (for example LDPE/HDPE).

3. Copolymers of monoolefins and diolefins with each other or with othervinyl monomers, for example ethylene/propylene copolymers, linear lowdensity polyethylene (LLDPE) and mixtures thereof with low densitypolyethylene (LDPE), propylene/but-1-ene copolymers, ethylene/hexenecopolymers, ethylene/ethylpentene copolymers, ethylene/heptenecopolymers, ethylene/octene copolymers, propylene/iso-butylenecopolymers, ethylene/but-1-ene copolymers, propylene/butadienecopolymers, isobutylene/isoprene copolymers, ethylene/alkyl acrylatecopolymers, ethylene/alkyl methacrylate copolymers, ethylene/vinylacetate or ethylene/acrylic acid copolymers and the salts thereof(ionomers), as well as terpolymers of ethylene with propylene and adiene, such as hexadiene, dicyclopentadiene or ethylidene-norbornene;and also mixtures of such polymers with one another and with polymersmentioned in 1) above, for example polypropylene/ethylene-propylenecopolymers, LDPE/ethylene-vinyl acetate copolymers (EVA),LDPE/ethylene-acrylic acid copolymers (EAA), LLDPE/EVA, LLDPE/EAA andalternating or random polyalkylene/carbon monoxide copolymers andmixtures thereof with other polymers, for example polyamides.

3a. Hydrocarbon resins (for example C₅ -C₉) including hydrogenatedmodifications thereof (for example tackifiers) and mixtures ofpolyalkylenes and starch.

4. Polystyrene, poly(p-methylstyrene), poly((α-methylstyrene).

5. Copolymers of styrene or α-methylstyrene with dienes or acrylicderivatives, for example styrene/butadiene, styrene/acrylonitrile,styrene/alkyl methacrylate, styrene/maleic anhydride,styrene/butadiene/alkyl acrylate, styrene/butadiene/alkyl methacrylatestyrene/acrylonitrile/methyl acrylate; mixtures of high impact strengthfrom styrene copolymers and another polymer, for example from apolyacrylate, a diene polymer or an ethylene/propylene/diene terpolymer;and block copolymers of styrene, for example styrene/butadiene/styrene,styrene/isoprene/styrene, styrene/ethylene/butylene/-styrene orstyrene/ethylene/propylene/ styrene.

6. Graft copolymers of styrene or α-methylstyrene, for example styreneon polybutadiene, styrene on polybutadiene-styrene orpolybutadiene-acrylonitrile copolymers; styrene and acrylonitrile (ormethacrylonitrile) on polybutadiene; styrene and maleic anhydride ormaleimide on polybutadiene; styrene, acrylonitrile and maleic anhydrideor maleimide on polybutadiene; styrene, acrylonitrile and methylmethacrylate on polybutadiene, styrene and alkyl acrylates ormethacrylates on polybutadiene, styrene and acrylonitrile onethylene/propylene/diene terpolymers, styrene and acrylonitrile onpolyacrylates or polymethacrylates, styrene and acrylonitrile onacrylate/butadiene copolymers, as well as mixtures thereof with thecopolymers listed in 5), for example the copolymer mixtures known asABS, MBS, ASA or AES polymers.

7. Halogen-containing polymers, such as polychloroprene, chlorinatedrubbers, chlorinated or chlorosulfonated polyethylene, copolymers ofethylene and chlorinated ethylene, epichlorohydrin homo- and copolymers,polymers of halogenated vinyl compounds, for example polyvinyl chloride,polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, aswell as copolymers thereof, for example vinyl chloride/vinylidenechloride, vinyl chloride/vinyl acetate or vinylidene chloride/vinylacetate copolymers.

8. Polymers derived from α,β-unsaturated acids and derivatives thereof,such as polyacrylates and polymethacrylates, polymethyl methacrylateimpact-modified with butyl acrylate, polyacrylamides andpolyacrylonitrile.

9. Copolymers of the monomers mentioned in 8) with each other or withother unsaturated monomers, for example acrylonitrile/butadiene,acrylonitrile/alkyl acrylate, acrylonitrile/alkoxyalkyl acrylate oracrylonitrile/vinyl halide copolymers or acrylonitrile/alkylmethacrylate/butadiene terpolymers.

10. Polymers derived from unsaturated alcohols and amines, or acylderivatives thereof or acetals thereof, such as polyvinyl alcohol,polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinylmaleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine;as well as their copolymers with olefins mentioned in 1) above.

11. Homopolymers and copolymers of cyclic ethers, such as polyalkyleneglycols, polyethylene oxide, polypropylene oxide or copolymers thereofwith bis(glycidyl) ethers.

12. Polyacetals such as polyoxymethylene and those polyoxymethyleneswhich contain ethylene oxide as a comonomer; polyacetals modified withthermoplastic polyurethanes, acrylates or MBS.

13. Polyphenylene oxides and sulfides and mixtures thereof with styrenepolymers or polyamides.

14. Polyurethanes derived from polyethers, polyesters orhydroxyl-terminated polybutadienes on the one hand and aliphatic oraromatic polyisocyanates on the other, as well as precursors thereof.

15. Polyamides and copolyamides derived from diamines and dicarboxylicacids and/or from aminocarboxylic acids or the corresponding lactams,such as polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6,12/12, polyamide 11, polyamide 12, aromatic polyamides obtained bycondensation of m-xylene diamine and adipic acid; polyamides preparedfrom hexamethylenediamine and isophthalic or/and terephthalic acid andoptionally an elastomer as modifier, for examplepoly-2,4,4,-trimethylhexamethylene terephthalamide or poly-m-phenyleneisophthalamide; and also copolymers of the aforementioned polyamideswith polyolefins, olefin copolymers, ionomers or chemically bonded orgrafted elastomers; or with polyethers, as with polyethylene glycols,polypropylene glycols or polytetramethylene glycols; polyamides orcopolyamides modified with EPDM or ABS; polyamides condensed duringprocessing (RIM polyamide systems).

16. Polyureas, polyimides, polyamide-imides and polybenzimidazoles.

17. Polyesters derived from dicarboxylic acids and diols and/or fromhydroxycarboxylic acids or the corresponding lactones, such aspolyethylene terephthalate, polybutylene terephthalate,poly-1,4-dimethylolcyclohexane terephthalate, poly2,2,-(4-hydroxyphenyl)propane!terephthalate and polyhydroxybenzoates aswell as block copolyether esters derived from hydroxyl-terminatedpolyethers; and also polyester modified with polycarbonates or MBS.

18. Polycarbonates and polyester carbonates.

19. Polysulfones, polyether sulfones and polyether ketones.

20. Polyethers of digylcidyl compounds, typically diglycidyl ethers anddiols, e.g. of the diglycidyl ether of bisphenol A and bisphenol A.

21. Natural polymers, such as cellulose, rubber, gelatin and chemicallymodified homologous derivatives thereof, such as cellulose acetates,cellulose propionates and cellulose butyrates, or the cellulose etherssuch as methyl cellulose; as well as rosins and their derivatives.

22. Blends of the aforementioned polymers (polyblends), for examplePP/EPDM, polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS,PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR,PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPE/HIPS, PPE/PA 66 andcopolymers, PA/HDPE, PA/PP, PA/PPO, PC/poly(epichlorohydrin).

Preferred thermoplastic polymers are polyolefins, polystyrene, polyvinylchloride, polyvinylidene chloride, polyvinylidene fluoride,polyacrylates, polymethacrylates, polyamides, polyesters,polycarbonates, aromatic polysulfones, aromatic polyethers, aromaticpolyether sulfones, polyimides and polyvinyl carbazole.

The thermosetting and structurally crosslinked polymers may be typicallythe following polymers:

1. Crosslinked polymers which are derived from aldehydes on the one handand phenols, ureas and melamines on the other hand, such asphenol/formaldehyde resins, urea/formaldehyde resins andmelamine/formaldehyde resins.

2. Drying and non-drying alkyd resins.

3. Unsaturated polyester resins which are derived from copolyesters ofsaturated and unsaturated dicarboxylic acids with polyhydric alcoholsand vinyl compounds as crosslinking, agents, and also halogen-containingmodifications thereof of low flammability.

4. Crosslinkable acrylic resins derived from substituted acrylic esterssuch as epoxy acrylates, urethane acrylates or polyester acrylates.

5. Alkyd resins, polyester resins or acrylate resins which arecross-linked with melamine resins, urea resins, polyisocyanates or epoxyresins.

6. Rubber derived from crosslinked polydienes, for example butadiene orisoprene; silicon rubber.

7. Epoxy resins which are derived from polyepoxides, for example frombisglycidyl ethers or from cycloaliphatic diepoxides, and which maycontain a hardener as crosslinking agent or which are crosslinkedthermally using curing accelerators or by irradiation.

Among the crosslinked polymers, crosslinked epoxy resins are preferredwhich, as poly-epoxides, are derived preferably from glycidyl compoundswhich contain on average two epoxy groups in the molecule. Particularlysuitable glycidyl compounds are those which contain two glycidyl groups,β-methylglycidyl groups or 2,3-epoxycyclopentyl groups attached to ahetero atom (e.g. sulfur, preferably oxygen or nitrogen), in particularbis(2,3-epoxycyclopentyl) ether; diglycidyl ethers of polyhydricaliphatic alcohols, such as 1,4-butanediol, or polyalkylene glycols,such as polypropylene glycols; diglycidyl ethers of cycloaliphaticpolyols, such as 2,2-bis(4-hydroxycyclohexyl)propane; diglycidyl ethersof polyhydric phenols, such as resorcinol, bis(p-hydroxyphenyl)methane,2,2-bis-(p-hydroxyphenyl)propane (═diomethane),2,2-bis(4'-hydroxy-3',5'-dibromophenyl)-propane,1,3-bis(p-hydroxyphenyl)ethane; bis(β-methylglycidyl) ethers of theabove dihydric alcohols or dihydric phenols; diglycidyl esters ofdicarboxylic acids, such as phthalic acid, terephthalic acid, Δ₄-tetrahydrophthalic acid and hexahydrophthalic acid; N,N-diglycidylderivatives of primary amines and amides and heterocyclic nitrogen baseswhich contain two N-atoms, and N,N'-diglycidyl derivatives ofdisecundary diamides and diamines, such as N,N-diglycidylaniline,N,N-diglycidyltoluidine, N,N-diglycidyl-p-aminophenyl methyl ether,N,N'-dimethyl-N,N'-diglycidylbis(p-aminophenyl)methane;N',N"-diglycidyl-N-phenyl-isocyanurate; N,N'-diglycidyl ethyleneurea;N,N'-diglycidyl-5,5-dimethylhydantoin,N,N'-diglycidyl-5-isopropyl-hydantoin,N,N-methylenebis-(N',N'-diglycidyl-5,5-dimethylhydantoin),1,3-bis(N-glycidyl-5,5-dimethylhydantoin)-2-hydroxypropane;N,N'-diglycidyl-5,5-dimethyl-6-isopropyl-5,6-dihydrouracil, triglycidylisocyanurate.

A preferred group of epoxy resins comprises glycidylated novolaks,hydantoins, aminophenols, bisphenols and aromatic diamines orcycloaliphatic epoxy compounds. Particularly preferred epoxy resins areglycidylated cresol novolaks, bisphenol A and bisphenol F diglycidylether, hydantoin-N,N'-bisglycide, p-aminophenol triglycide,diaminodiphenylmethane tetraglycide, vinylcyclohexene dioxide,3,4-epoxycyclohexyl-methyl-3,4-epoxycyclohexanecarboxylate or mixturesthereof.

Further suitable epoxy resins are prereacted adducts of such epoxycompounds with epoxy hardeners, for example an adduct of bisphenol Adiglycidyl ether and bisphenol A, or adducts which have been prereactedwith oligoesters which carry two terminal carboxyl groups and epoxides.

Suitable hardeners for epoxy resins are acid or basic compounds.Illustrative examples of suitable hardeners are: polyhydric phenols(resorcinol, 2,2-bis(4-hydroxyphenyl)propane) or phenol-formaldehyderesins; polybasic carboxylic acids and the anhydrides thereof, such asphthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalicanhydride, 4-methylhexahydrophthalic anhydride,3,6-endomethylene-tetrahydrophthalic anhydride,4-methyl-3,6-endomethylen-tetrahydrophthalic anhydride (methylnadicanhydride), 3,4,5,6,7,7-hexachloroendomethylene-tetrahydrophthalicanhydride, succinic anhydride, adipic anhydride, trimethyladipicanhydride, sebacic anhydride, maleic anhydride, dodecylsuccinicanhydride, pyromellitic dianhydride, trimellitic anhydride,benzophenonetetracarboxylic dianhydride, or mixtures of such anhydrides.

A preferred group of hardeners comprises novolaks and polycarboxylicanhydrides.

The epoxy resins can also be additionally cured with curing acceleratorsor only with thermal curing catalysts. Exemplary of curing acceleratorsand catalysts are 3-ethyl-4-methylimidazole, triamylammonium phenolate;mono- or polyphenols (phenol, diomethane, salicylic acid); borontrifluoride and the complexes thereof with organic compounds, such asboron trifluoride ether complexes and boron trifluoride amine complexes(BF₃ /monoethylamine complex); phosphoric acid and triphenylphosphite.

Curing accelerators and catalysts are normally added in an amount of 0.1to 10% by weight, based on the epoxy resin. Hardeners for epoxy resinsare normally used in equimolar amounts, based on the epoxy groups andfunctional groups of a hardener.

Thermosetting or crosslinked polymers are also photo resists, X-rayresists, electron and ion beam resists and photopolymers. Examples ofsuitable radiation polymerized polymers are as follows (see, forexample, A. Reiser, Photoreactive Polymers, John Wiley & Sons, New York(1989)):

1. Negative resists, such as dichromated polymers, e.g., dichromatedgelatine, starch, poly(vinyl alcohol), poly(vinylpyrrolidone),poly(vinyl butyral) and poly(amide acid); polymers having crosslinkinggroups in side chains, such as poly(vinyl cinnamate), poly(vinylcinnamylidene acetate), poly(vinyl alcohol) to which chalcone orphenylene diacrylate are attached and polyesters of p-phenylenediacrylicacid with glycols; water processable resists such as styrene-maleicanhydride copolymer, phenolic quatenary pyridinium salts, polymericstyrylquinolinium salts; bis-azide resists based on poly(cis-isoprene)and bis-azides, such as 2,6-bis(4-azidobenzal)-4-methylcyclohexanone,4,4'-diazidostilbene, 4,4'-diazidobenzophenone and4,4'-diazidobenzalacetone; water processable azido resists based onpoly(acrylamide) or poly(vinylpyrrolidone) and water soluble bis-azides;azide resists based on poly(vinyl phenol) and mono-azides; poly(vinylalcohol) and poly(vinylpyridine) to which a bifunctional acrylsilane isadded; photocrosslinking copolymers of vinyl benzophenone and4-dimethylaminostyrene; as well as crosslinked polymers from thesepolymers.

2. Photopolymers containing monomers, such as acrylates, methacrylates,acrylamide and styrene, crosslinkers, such as 1,6-hexanediol diacrylate,triethyleneglycol diacrylate, N,N'-methylenebis(acrylamide),trimethylolpropanetriacrylate, pentaerythritol triacrylate andpentaerythritol tetraacrylate, binders such as polymers of the monomersused, polyesters, polyurethanes, nylons, polycarbonates and cellulosederivatives, fillers such as organophilic silicates and clays,initiators such as benzoin derivatives, anthraquinone plus hydrogendonors, and benzophenones and amines, and stabilisers, such asp-methoxyphenol, hydroquinones and naphthols; especially thosecontaining reactive binders such as unsaturated polymers obtained by thecondensation of maleic and fumaric acid with glycols, polyfunctionalacrylates based on bisphenol A or a polyfunctional prepolymers; as wellas crosslinked polymers of these photopolymers.

3. Positive resists, such as diazoquinone resists based on phenolicresins, e.g., novolak and diazonaphthoquinones.

4. Positive deep-UV resists, such as modified diazoquinone resist basedon novolak and diazopyrazolidine dione, diazotetramic acid,diazopiperidine dione and diazo-Mendrum's acid; resists based ono-nitrobenzyl esters; o-nitrobenzyl-substituted polyethers;m-polynitroanilide; poly(p-acetoxystyrene); poly(methyl methacrylate)derivatives, such as 3-oximono-2-butanone methacrylate (OMMA)-methylmethacrylate copolymer, OMMA-methacrylonitrile-methyl methacrylateterpolymer, methyl methacrylate-indene-copolymer;poly(methylisopropylketone); polymers containing triphenylcarbonium ionin their backbone; poly(tert-butoxycarbonyloxystyrene), preferably withan onium salt acid generator; novolak with carbonates and onium salt orwith naphthalene-2-carboxylic acid-tert-butyl ester; copolymers ofphthalaldehyde with o-nitrobenzaldehyde.

5. Negative deep-UV resists, such as bis-azide-cyclized rubbercomposition containing 4,4'-diazidodiphenyl sulfide,bis-azido-poly(vinyl phenol) composition containing 3,3'-diazidodiphenylsulfon and bis-azido-poly(methyl methacrylate) composition containing3,3'-diazidodiphenyl sulfon, epoxides with onium salts or withn-hexyloxydiazonium hexafluorophosphate.

6. Positive electron resists, such as PMMA derivatives, e.g.,poly(perfluorobutyl methacrylate), poly(hexafluoromethacrylate) andespecially poly(2,2,2-trifluoroethyl-α-chloroacrylate); copolymers ofMMA with methacrylic acid, acrylonitrile or methacrylic anhydride;terpolymers of MMA, methacrylic acid and methacrylic anhydride;poly(olefine sulfones), such as poly(butene sulfon); novolaks withpoly(olefine sulfon), such as poly(2-methylpentene-1-sulfon);poly(p-tert-butoxycarbonyl oxystarene); poly(ortho-substituted2-phenylethyl methacrylates); polystyrene-tetrathiofulvalene.

7. Negative electron resists, such as epoxydized poly(butadiene),poly(glycidyl methacrylate), copolymers of glycidyl methacrylate withethylacrylate; copolymers of allyl methacrylate with hydroxyethylmethacrylate; copolymers of propargyl methacrylate with hydroxyethylmethacrylate; polystyrene based resists, such as iodonated polystyreneand poly(chloromethylstyrene); poly(vinyl naphthalenes);poly(chloromethylstyrene-co-2-vinyl naphthalene); poly(vinyl pyridine)quaternized with methyl iodine; diazoquinone-novolak photoresists; aswell as crosslinked polymers from these polymers.

8. Positive X-ray resists, such as Olin-Hunt resist HPR-204 (acommercial product).

9. Negative X-ray resists, such as poly(2,3-dichloro-1-propyl acrylate),poly(chloromethylstyrene), chlorinated polymethylstyrene, copolymers ofallyl methacrylate with 2-hydroxyethyl methacrylate orglycidylmethacrylate; crosslinked polymers from these polymers.

10. Positive ion beam resists, such as poly(methyl methacrylate),poly(methylvinyl ketone), poly(tert-butyl methacrylate) and poly(butenesulfone).

11. Negative ion beam resists, such as poly(vinyl acetate), poly(vinylcinnamate), poly(methyl siloxane), poly(glycidyl methacrylate-co-ethylacrylate), poly(styrene), poly(4-chlorostyrene), poly(4-bromostyrene)and novolaks; crosslinked polymers from these polymers.

12. Silicon-containing positive resists, such as poly(dimethylsiloxane),poly(phenylmethylsiloxane) and siloxane-substituted propylmethacrylates.

13. Silicon-containing negative resists, such as copolymers oftrimethylsilylmethylstyrene with chlorostyrene, chloromethylatedpolydiphenyl siloxane, brominated poly(1-trimethylsilyl propylene),poly(triallylphenylsilane) together with2,6-bis(4'-azidobenzal)-methylcyclohexanone, andpoly(trimethylsilylmethylstyrene) in combination with1,2,4-trichlorobenzene and 3,3'-diazidodiphenyl sulfone; as well ascrosslinked polymers from these polymers.

These photo-, X-ray, electron- and ion beam resists and photopolymersare well known in the art.

The composition of the present invention can be produced by simplymixing a thermoplastic polymer (or a prepolymer or monomer component ofa thermosetting or cross-linkable polymer), an electron donor and anelectron acceptor, either the electron donor or the electron acceptorbeing weakly-soluble in said polymer, prepolymer or monomer, thenaccomplishing an in-situ reaction by the introduction of energy (heatand/or actinic radiation) to this reaction mixture, and finallycrosslinking the polymer, if necessary.

The production of the composition of the present invention does not needany solvent.

In the above process, an electroconductive network system comprisinguniformly distributed finely divided particles of the polymerweakly-soluble component and crystals of the CT-crystals crown fromthese particles is formed, whereby the crystal needles penetrate thepolymer mass.

Another object of the instant invention is a process for the preparationof the above described composition, characterized in that

(1) either at least one finely divided weakly polymer-soluble electronacceptor or electron donor is dispersed and uniformly distributed in amolten thermoplastic and at least one polymer-soluble electron acceptoror at least one polymer-soluble electron donor is dissolved in themolten thermoplastic polymer; or

(2) either at least one finely divided weakly polymer-soluble electronacceptor or electron donor is dispersed and uniformly distributed in atleast one monomer or prepolymer component of a thermosetting orstructurally cross-linkable polymer and at least one polymer-solubleelectron acceptor or at least one polymer-soluble electron donor isdissolved in one and the same or in another monomer or prepolymercomponent of a thermosetting or structurally cross-linkable polymer, andpolymerizing the mixture optionally together with further monomer orprepolymer components of a thermosetting or structurally cross-linkablepolymer; and

(3) heating the polymer composition for a time sufficient to form thenetwork of crystal needles.

The electron donor is used in an amount of 10⁻³ to 2% by weight,preferably 10⁻¹ to 1% by weight, based on the thermoplastic polymer orthe prepolymer or monomer component of the thermosetting orcrosslinkable polymer. The electron acceptor is used in an amount of10⁻³ to 2% by weight, preferably 10⁻² to 1% by weight, based on theelectron donor. If the electron donor is a compound of theaforementioned formula I or Ia and the thermoplastic polymer or theprepolymer or monomer component of the thermosetting or crosslinkablepolymer is a halogen-containing one, it is not necessary to add anelectron acceptor. For example, if the thermoplastic polymer ispolyvinyl chloride, polychloroprene, polyvinylidene chloride or thelike, it is not necessary to add an electron acceptor.

The particle size of the weakly polymer-soluble electron donor oracceptor is 10 nm to 20 μm, most preferably 50 nm to 5 μm.

If the polymer matrix is to be made of a thermoplastic polymer, thethermoplastic polymer is firstly fused at a temperature higher than itsmelting point and lower than its decomposition temperature, to which theelectron donor and the electron acceptor, either the electron donor orthe electron acceptor being finely divided, weakly polymer-solubleparticles and the other being polymer-soluble, are added in such amanner that the weakly polymer-soluble component is dispersed anduniformly distributed (step (1)). Then this mixture is moulded by aconventional method, such as injection, extrusion, pressing and calendermoulding, at a temperature and for a time sufficient for forming thenetwork of crystal needles (step (3)). The moulding is accomplished at atemperature of 100° to 350° C., preferably 120° to 250° C. for 5 minutesto 2 hours, preferably 10 minutes to 30 minutes hours. The abovemixture, composed of the fused thermoplastic polymer, the electron donorand the electron acceptor, may also be coated on a suitable substrate,such as a glass plate, photofilm or a printed circuit board and, then,subjected to the formation of the network of crystal needles. Preferredconditions for the network formation are the same as those mentionedabove.

If the polymer matrix is to be made of a thermosetting or structurallycrosslinked polymer, the electron donor and the electron acceptor,either the electron donor or the electron acceptor beingweaklypolymer-soluble and the other being polymer-soluble, are added toat least one monomer or prepolymer component of a thermosetting orstructurally crosslinkable polymer in such a manner that the weaklypolymer-soluble component is uniformly dispersed in the monomer orprepolymer component. Herein, it is understood that "weaklypolymer-soluble" means weakly monomer-soluble (weaklyprepolymer-soluble) and "polymer-soluble" means monomer-soluble(prepolymer-soluble). The electron donor and the electron acceptortogether can be added to the same monomer or prepolymer component, orthey can each be added to different monomer or prepolymer components. Inthe latter case, the two mixtures are subsequently mixed with eachother. When the monomer or prepolymer component consists of a pluralityof monomers and/or prepolymers, the monomer of prepolymer ingredientsare selected such that they yield a copolymer satisfying the desiredmaterial properties, e.g. transparency, thermal expansion, tensilestrength, elasticity, heat resistance, chemical resistance and flameresistance. If necessary, further monomers or prepolymers of athermosetting or structurally cross-linkable polymer may be added. Thenomomer or prepolymer component is then polymerized (step (2)).

If the monomer or prepolymer component is that of a thermosettingpolymer, the polymerization and the formation of the network of crystalneedles (step(3)) are carried out preferably by means of the moulding orcoating method as described above. Preferred temperatures for thermalpolymerization are well known in the art for each thermosetting polymer.Preferred temperatures for the formation of crystal needles are alreadymentioned in the above. However, if the crystal needle formation takesplace during the polymerization of the monomer or prepolymer component,it is not necessary to further heat the composition for this purpose.This can be assessed easily by microscopic observation.

If the monomer or prepolymer component is a photopolymer or aphotoresist, the above prepared system, consisting of the monomer orprepolymer component, the electron donor and electron acceptor, ispreferably applied to a suitable substrate such as a glass plate, aprinted circuit board or any article whose surface is to be madeelectroconductive. The polymerization of the monomer or prepolymercomponent is effected by actinic radiation and simultaneous heating orheating after radiation. Preferred conditions of radiation and heatingare well known in the art. Preferred temperatures and duration ofheating for the formation of the network of crystal needles are alreadygiven above.

The moulding method is suitable for the production of electroconductiveformed articles, whilst the coating method is advantageous for theproduction of electroconductive composites such as laminates comprisinga dielectric film and an electroconductive or antistatic film or for theproduction of electroconductive or antistatic coating.

In the above process for the preparation of the composition of theinstant invention, when one selected from the group consisting ofhalogen-containing organic compounds, including halogen-containingmonomers, prepolymers and polymers and halogen containing matrixpolymers, is used as an electron acceptor, the system prepared in step(1) or (2) is heated at a temperature between room temperature and 350°C., preferably from 50° to 200° C., in order to cleave the halogen atomsso that they effectively form CT-crystals with the incorporated electrondonor.

The thus produced composition of the present invention usually shows anelectroconductivity of 10⁻¹⁰ to 10 S/cm depending on the CT complex, itsconcentration and the type of the donor.

In the present invention, it is always possible to form anelectroconductive network of percolated CT-crystals at any concentrationof the polymer weakly-soluble component (donor or acceptor). If theCT-crystals growing from the polymer weakly-soluble component are notlong enough to achieve percolation, the percolation can be achieved byreducing the initial particle size of the polymer weakly-solublecomponent. Therefore, electroconductivity ranging from 10⁻¹⁰ to 10 S/cmas mentioned above is readily achieved.

Because of the simplicity in controlling electroconductivity, thecomposition of the present invention can be applied in various fields inaccordance with the required electroconductivity in form of mouldedarticles, such as electroconductive bulk articles, e.g. conveyer belts,pipes, bags, flooring plates, electrodes and electroconductors, or aselectroconductive composites, such as laminates comprising a dielectricmaterial e.g. a photofilm and an electroconductive or antistatic film,or for the production of electroconductive or antistatic coatings. Inparticular, the composition of the present invention is preeminentlysuitable for use as transparent antistatic films with small haze problemsince networks of percolated CT-crystals, the crystals having across-section diameter smaller than that of light wavelength, can easilybe formed at such low donor and acceptor concentrations that practicallydo not affect the transparency of the films. Moreover, since thecomposition of the present invention is produced in an in-situ processwithout using any solvent, the method for the production of the instantcomposition is environment very safe.

The difference between the composition of the instant invention and aprior art composition is shown in FIGS. 1 and 3. The prior artcomposition comprises a polymer matrix and an electroconductive net-workof crystal needles of a CT complex without any weakly polymer-solubleelectron donor and acceptor. FIG. 1 is a microscope image of acomposition of the instant invention comprising a low densitypolyethylene matrix, tetrathiotetracene as weakly polymer-solubleelectron donor particles and a CT complex of said tetrathiotetracenewith a polymer-soluble electron accepetor tetrahexylammonium-CuCl₂(obtained from Example 1 below). FIG. 3 is a microscope image of theprior art composition comprising a phenoxy resin matrix and a CT complexof tetrathiotetracene with CuCl₂ (0.5% tetrathiotetracene-(CuCl₂)₀.45 inphenoxy resin, sprayed from a solution). FIG. 1 clearly shows thatcrystal needles grow from the weakly polymer-soluble particles and areformed in the polymer mass as microcrystalline needles, which are incontact and connect the weakly polymer-soluble particles, thus forming anetwork which penetrates the polymer mass, while FIG. 3 shows only anetwork of needle crystals of the CT complex. FIG. 2 shows another wayto achieve percolation according to the instant invention (obtained fromExample 2 below), where a star-like growth out of the seed crystal isobtained.

EXAMPLES Example 1

Preparation of electroconductive network by reaction oftetrathiotetracene-particles with tetrahexylammonium-CuCl₂ in lowdensity poly(ethylene)

50 g of low density poly(ethylene) (hereinafter, referred to as LD-PE,Lupolen 1840D) together with 1 wt % tetrathiotetracene (hereinafter,referred to as TTT, 0.1-5 μm in particle size) and 1.5 wt %tetrahexylammonium-CuCl₂ (hereinafter, referred to as THACuCl₂) aremixed in a mixer, and this mixture is processed on calender at atemperature of 120° C. for 5 minutes. The thus prepared foil is cut intopieces, and a plate is prepared therefrom under a press under heating at160° C. for 5 minutes. The obtained 2 mm thick plate is homogeneous andhas a green color. A portion of this plate is placed under a ReichertHot Microscope and heated to 180° C. The formation of needle crystals,which begins after 15 minutes, is documented and is complete after about2 hours. It is observed that a dense, percolated and electroconductivenetwork is formed. The surface resistance of this composition determinedby the two-probe method is 10⁶ Ohm. (Two Pt-paste electrodes of 1 cmlength are painted 0.2 cm apart on the surface.)

Example 2

Preparation of needle networks from TTT and CuCl₂ crystals by reactionof CuCl₂ -particles with TTT

Finely milled CuCl₂ -salt (anhydous) having a particle size of 0.5-3 μmis placed on a glass plate coated with a gelatin (Fluka, low gelstrength) layer. (The gelatin layer is provided in order to fix theparticles so that they are not lost during the following process.) Thena saturated TTT-solution (anisole; 0.2 g TTT/l) is slowly applied to thegelatine layer, and the crystal growth is observed under a microscopeand documented. The crystal growth is complete after about 1 hour atroom temperature. It is observed that star-like crystals are formed.These crystals form a percolated electroconductive network. Thesurface-resistance of this composition determined by two-probe method is10⁸ Ohms. (The electrodes are formed in the same way as in Example 1.)

What is claimed is:
 1. A composition comprising a matrix of athermoplastic, thermosetting or a structurally crosslinked polymer, inwhich is incorporated an electroconductive network of crystal needles ofa charge transfer complex (abbreviated to CT complex) from an electrondonor and an electron acceptor, characterized in that(1) the matrixcontains uniformly distributed an excess, with respect to the CT complexformation, either of at least one electron donor or at least oneelectron acceptor as weakly polymer-soluble finely divided particles,(2) the CT complex is formed either by at least one weaklypolymer-soluble electron donor and at least one polymer-soluble electronacceptor or by at least one weakly polymer-soluble electron acceptor andat least one polymer-soluble electron donor, and (3) microcrystallineneedles grow from the weakly polymer-soluble particles in the polymermass, which microcrystalline needles, are in contact with and connectthe weakly polymer-soluble particles to form a network which penetratesthe polymer mass;wherein said electron acceptor is a halogen-containingorganic compound selected from the group consisting oftetrabromomethane, bromoform, trichlorobromomethane, hexachloropropane,hexachloropropene, hexachlorocyclopropane, hexachlorocyclopentadiene,hexachloroethane, N-chlorosuccinimide, octachloropropane,n-octachlorobutane, n-decachlorobutane, tetrabromoethane,hexabromoethane, tetrabromobenzoquinone,2,4,4,6-tetrabromo-2,5-cyclohexadienone, hexabromobenzene, chloranil,hexachloroacetone, 1,4,5,6,7,7-hexachloro-5-norbornen-2,3-dicarboxylicacid, 1,2,5,6,9,10-hexabromocyclododecane, tetrachloroethylene,perchlorocyclopentadiene, perchlorobutadiene,dichloroacetaldehyde-diethylacetal, 1,4-dichloro-2-butene,1,3-dichloro-2-butene, 3,4-dichloro-1-butene, tetrachlorocyclopropane,1,3-dichloroacetone, 2,3,5,6-hexachloro-p-xylene,1,4-bis(trichloromethyl)-benzene, 1,3-dibromopropane, 1,6-dibromohexane,3-chloropropionic acid ethylester, 3-chlorotoluene, 2-chloropropionicacid methylester, 2-chloroacrylonitrile, trichloroacetic acidethylester, 1,2,3-trichloropropane, 1,1,2-trichloroethane, chloroformicacid butylester, trichloroethylene, 2,3-dichloromaleic anhydride,1,12-dibromododecane, α,α'-dibromo-p-xylene, α,α'-dichloro-o-xylene,phenacylchloride or-bromide, 1,10-dibromodecane, α,α'-dichloro-p-xylene,α,α'-dibromo-m-xylene, iodoacetonitrile,2,3-dichloro-5,6-dicyanobenzoquinone, 2,3-dichloropropionic acidmethylester, 1-bromo-2-chloroethane, 1-bromo-2-chloropropane,chloroformic acid-2-bromoethylester, iodoacetic acid ethylester,N-chloro-, N-bromo- or N-iodosuccinimide or -phthalimide, and mixturesthereof.
 2. A composition according to claim 1, wherein the diameter ofsaid particles lies between 10 nm to 20 μm.
 3. A composition accordingto claim 1, wherein said crystals of a CT complex are contained in thepolymer matrix in an amount of 10⁻³ to 2% by weight, based on thepolymer.
 4. A composition according to claim 1, wherein said crystalshave a length of 0.1 μm to 1000 μm, and an aspect ratio (length:widthratio) of 1 to
 10000. 5. A composition according to claim 1, whereinsaid electron donor is at least one compound of formula I or Ia or amixture thereof ##STR23## wherein X₁ is S, Se or Te, R₁, R₂, R₃ and R₄are each independently of one another H or Cl, or R₁ and R₂ as well asR₃ and R₄ are each mean ##STR24## R₁, R₂, R₃ and R₄ are eachindependently of one another phenylthio, 4-methyl- or4-methoxyphenylthio or 4-pyridylthio, R₅, R₆, R₇ and R₈ mean eachindependently of the other H or F, R₅ is CH₃ and R₆, R₇ and R₈ are H orR₅, R₆, R₇ and R₈ are CH₃, R₅ and R₆ are CH₃ or Cl and R₇ and R₈ are Hor R₅ and R₆ are H, R₇ is --COR₉ and R₈ is H or --COR₉, or R₅ and R₆ areH and R₇ and R₈ together are --CO--O--CO or --CO--NR₁₀ --CO--, R₉ ishalogen, --OH, --NH₂, or the residue of an alcohol or of primary orsecondary amine, or --OM, M being a cation and R₁₀ stands for H or theresidue of a primary amine which is diminished by NH₂ -- group.
 6. Acomposition according to claim 5, wherein said compound represented byformula I or Ia is 5,6,11,12-tetrathiotetracene,5,6,11,12-tetraselenotetracene, 2-fluoro- or2,3-difluoro-5,6,11,12-tetraselenotetracene,2,3,8,9-tetramethyl-5,6,11,12-tetrathiotetracene,2,3,8,9-tetramethyl-5,6,11,12-tetraselenotetracene,2-methyl-5,6,11,12-tetrathiotetracene,2,3,8,9-tetrafluoro-5,6,11,12-tetrathiotetracene,2,3,8,9-tetrafluoro-5,6,11,12-tetraselenotetracene,2,3-dichloro-5,6,11,12-tetraselenotetracene,2-fluoro-5,6,11,12-tetratellurotetracene,2,3,6,7-tetrathiophenyl-1,4,5,8-tetrathionaphthalene,2,3,6,7-tetramethoxyphenyl-1,4,5,8-tetrathionaphthalene,2,3,6,7-tetra-4-pyridylthio-1,4,5,8-tetrathionaphthalene,2,3,6,7-tetraphenylthio-1,4,5,8-tetraselenonaphthalene, or the compound##STR25##
 7. A composition according to claim 1, wherein said electrondonor is at least one compound represented by formula II ##STR26##wherein R₁₁, R₁₂, R₁₃ and R₁₄ are each independently of one another C₁-C₁₂ -alkyl, phenyl, C₁ -C₁₂ -alkylphenyl, C₁ -C₁₂ -alkoxyphenyl or H,or R₁₁ and R₁₂ together are a residue of ##STR27## --(CH₂)_(p) --,--C(CH₃)₂ --(CH₂)_(p) --C(CH₃)₂ -- or --S--(CH₂)_(p) --S--, p is aninteger 1-12 and R₁₃ and R₁₄ are each independently of the other C₁ -C₁₂-alkyl, phenyl, C₁ -C₁₂ -alkylphenyl, C₁ -C₁₂ -alkoxyphenyl orespecially H, or R₁₁ and R₁₂ are each independently of the other C₁ -C₁₂-alkyl, phenyl, C₁ -C₁₂ -alkylphenyl, C₁ -C₁₂ -alkoxyphenyl or H and R₁₃and R₁₄ together are a residue of ##STR28## --(CH₂)_(p) --, --C(CH₃)₂--(CH₂)_(p) --C(CH₃)₂ -- or --S--(CH₂)_(p) --S--, p is an integer 1-12,and X₂, X₃, X₄ and X₅ are Se or S.
 8. A composition according to claim1, wherein said electron donor is at least one compound of formula III##STR29## wherein X₆ is S, Se or N--C₁ -C₁₂ -alkyl and R₁₅ is H, C₁ -C₁₂-alkyl or substituted or unsubstituted phenyl.
 9. A compositioncomprising a matrix of a thermoplastic, thermosetting or a structurallycrosslinked polymer, in which is incorporated an electroconductivenetwork of crystal needles of a charge transfer complex (abbreviated toCT complex) from an electron donor and an electron acceptor,characterized in that(1) the matrix contains uniformly distributed anexcess, with respect to the CT complex formation, either of at least oneelectron donor or at least one electron acceptor as weaklypolymer-soluble finely divided particles, (2) the CT complex is formedeither by at least one weakly polymer-soluble electron donor and atleast one polymer-soluble electron acceptor or by at least one weaklypolymer-soluble electron acceptor and at least one polymer-solubleelectron donor, and (3) microcrystalline needles grow from the weaklypolymer-soluble particles in the polymer mass, which microcrystallineneedles are in contact with and connect the weakly polymer-solubleparticles to form a network which penetrates the polymer mass;whereinsaid electron acceptor is a halogen-containing organic compound selectedfrom the group consisting of halogen-containing thermoplastic polymercontaining aliphatic or cycloaliphatic side groups, which side groupsare bound to the polymer backbone via a group --O--, --O--CO--,--CO--OA--OCO-- or --CO--O-- and contain at least one Cl-, Br- or I-atomin α-, β-, γ- or ω-position, wherein A is C₂ -C₁₂ -alkylene, C₄ -C₁₂-cycloalkylene, C₄ --C₁₂ -cycloalkylene-CH₂ --, C₄ -C₁₂-cycloalkylene-(CH₂)₂ --, benzylene or xylylene, which is unsubstitutedor substituted by OH, Cl, Br or phenyl.
 10. A composition according toclaim 9, wherein the groups --O, --O--CO--, --CO--OA--O--CO-- or--CO--O-- have groups of the formula --C_(m) H_(n) Y_(o) bonded to them,wherein m is a number from 1 to 12, n is 0 or a number from 1 to 24, ois a number from 1 to 25 and n+o=2m+1, Y is Cl, Br or I and A is C₂ -C₁₂-alkylene, C₄ -C₁₂ -cycloalkylene, C₄ -C₁₂ -cycloalkylene-CH₂ --, C₂-C₁₂ -cycloalkylene-(CH₂)₂ --, benzylene or xylylene which isunsubstituted or substituted by OH, Cl, Br or phenyl.
 11. A compositionaccording to claim 9, wherein said thermoplastic polymer is a linearpolyadduct of a glycidyl compound containing an average of more than oneepoxy group, and a diol, a primary monoamine, a di-secondary diamine, adi-secondary linear or cyclic dicarboxylic acid diamide or adicarboxylic acid, in which polyadduct the H atom of the secondary OHgroups is at least partially substituted by a group --CO--C_(m) H_(n)Y_(o), wherein m is a number from 1 to 12, n is 0 or a number from 1 to24, o is a number from 1 to 25 and n+o=2m+1, and Y is Cl, Br or I.
 12. Acomposition according to claim 9, wherein said thermoplastic polymer isa polyadduct containinga) 100 to 0.1 mol % of identical or differentstructural units of formula IV ##STR30## and b) 99.9 to 0 mol % ofidentical or different structural units of formula V ##STR31## based onthe polyadduct, wherein A₁ and A₂ are each independently of the otherthe radical of a diol containing aliphatic or aromatic diol groups, fromwhich two hydroxyl groups have been removed, A' is H, unsubstituted orOH-substituted C₁ -C₂₀ -alkyl, C₁ -C₂₀ -acyl or aminocarbonylN-substituted by a C₁ -C₂₀ -hydrocarbon radical, --OA₃ -- is a directbond or A₃ is ethylene which is unsubstituted or substituted by C₁ -C₁₆-alkyl.
 13. A composition according to claim 12, wherein A₁ and A₂ areeach independently of the other a radical of the formula ##STR32##wherein Y₁ is a direct bond, C₁ -C₄ -alkylene, C₂ -C₁₂ -alkylidene, C₅-C₈ -cycloalkylidene, --O--, --S--, --SO--, --SO₂ --, --CO--, --CO₂ --,--N(C₁ -C₄ -alkyl)- or --Si(CH₃)₂ --, A₄ and A₅ are independently of theother H, halogen, C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy, x is 0, 1 or 2 and yis 0 or
 1. 14. A composition according to claim 12, wherein A₁ and A₂are the radical ##STR33##
 15. A composition according to claim 9,wherein the thermoplastic polymer containsa) 0.1 to 100 mol % of atleast one structural unit of formula VI ##STR34## and b) 0 to 99.9 mol %of at least one structural unit of formula VII ##STR35## based on thepolymer, wherein A₆ is H or methyl; A₇ is a radical --(A--O--CO)_(z)--C_(m) H_(n) Y_(o), wherein z is 0 or 1, m is a number from 1 to 12, nis 0 or a number from 1 to 24, o is a number from 1 to 25 and n+o=2m+1,Y is Cl, Br or I and A is C₂ -C₁₂ -alkylene, C₄ -C₁₂ -cycloalkylene, C₄-C₁₂ -cycloalkylene-CH₂ --, C₂ -C₁₂ -cycloalkylene-(CH₂)₂ --, benzyleneor xylylene which is unsubstituted or substituted by OH, Cl, Br orphenyl; A₈ is H, C₁ -C₆ -alkyl or --COOA₁₁ ; A₉ is H, F, Cl, CN or C₁-C₆ -alkyl; and A₁₀ is H, F, Cl, CN, A₁₁ --O--, C₁ -C₁₂ -alkyl,--COOA₁₁, --O--CO--, --A₁₁, --COOA--OH, ##STR36## or phenyl, wherein Ais as defined above and A₁₁ is C₁ -C₁₈ -alkyl, C₅ -C₇ -cycloalkyl, (C₁-C₁₂ -alkyl)-C₅ -C₇ -cycloalkyl, phenyl, (C₁ -C₁₂ -alkyl)phenyl, benzylor (C₁ -C₁₂ -alkyl)benzyl.
 16. A composition according to claim 9,wherein the thermoplastic polymer containsa) 90 to 0.1 mol % ofstructural units of formula VIII ##STR37## and b) 99.9 to 10 mol % ofidentical or different structural units of formula IX ##STR38## whereinZ is a direct bond, --CO-- or --A₃ --O--CO--, A₃ being ethylene which isunsubstituted or substituted by C₁ -C₁₆ -alkyl; Y is Cl, Br or I; m is anumber from 1 to 12, n is 0 or a number from 1 to 24, o is a number from1 to 25 and n+o=2m+1; A₁₂ is H, C₁ -C₆ -alkyl or --COOA₁₁ ; A₉ is H, F,Cl, CN or C₁ -C₆ -alkyl; and A₁₂ is H, F, Cl, CN, OH, A₁₁ O--, C₁ -C₁₂-alkyl, --COOA₁₁, --O--CO--A₁₁, --OAOH or phenyl, A₁₁ being C₁ -C₁₈-alkyl, C₅ -C₇ -cycloalkyl, (C₁ -C₁₂ -alkyl)-C₅ -C₇ -cycloalkyl, phenyl,(C₁ -C₁₂ -alkyl)phenyl, benzyl or (C₁ -C₁₂ -alkyl)benzyl and A beingethylene which is unsubstituted or substituted by C₁ -C₁₆ -alkyl.
 17. Acomposition comprising a matrix of a thermoplastic, thermosetting or astructurally crosslinked polymer, in which is incorporated anelectroconductive network of crystal needles of a charge transfercomplex (abbreviated to CT complex) from an electron donor and anelectron acceptor, characterized in that(1) the matrix containsuniformly distributed an excess, with respect to the CT complexformation, either of at least one electron donor or at least oneelectron acceptor as weakly polymer-soluble finely divided particles,(2) the CT complex is formed either by at least one weaklypolymer-soluble electron donor and at least one polymer-soluble electronacceptor or by at least one weakly polymer-soluble electron acceptor andat least one polymer-soluble electron donor, and (3) microcrystallineneedles grow from the weakly polymer-soluble particles in the polymermass, which microcrystalline needles are in contact with and connect theweakly polymer-soluble particles to form a network which penetrates thepolymer mass;wherein said electron acceptor is at least one salt of anoxidatively acting cation of a transition metal or rare earth metal witha non-nucleophilic anion selected from the group consisting of halogen(F.sup.⊖, Cl.sub.⊖), BF₄.sup.⊖, SbF₆.sup.⊖, AsF₆.sup.⊖ and PF₆.sup.⊖.18. A composition comprising a matrix of a thermoplastic, thermosettingor a structurally crosslinked polymer, in which is incorporated anelectroconductive network of crystal needles of a charge transfercomplex (abbreviated to CT complex) from an electron donor and anelectron acceptor, characterized in that(1) the matrix containsuniformly distributed an excess, with respect to the CT complexformation, either of at least one electron donor or at least oneelectron acceptor as weakly polymer-soluble finely divided particles,(2) the CT complex is formed either by at least one weaklypolymer-soluble electron donor and at least one polymer-soluble electronacceptor or by at least one weakly polymer-soluble electron acceptor andat least one polymer-soluble electron donor, and (3) microcrystallineneedles grow from the weakly polymer-soluble particles in the polymermass, which microcrystalline needles are in contact with and connect theweakly polymer-soluble particles to form a network which penetrates thepolymer mass;wherein said electron acceptor is selected from the groupconsisting of CuCl₂ and CuBr₂ and their aquo, solvent or ammoniumcomplexes.
 19. A composition comprising a matrix of a thermoplastic,thermosetting or a structurally crosslinked polymer, in which isincorporated an electroconductive network of crystal needles of a chargetransfer complex (abbreviated to CT complex) from an electron donor andan electron acceptor, characterized in that(1) the matrix containsuniformly distributed an excess, with respect to the CT complexformation, either of at least one electron donor or at least oneelectron acceptor as weakly polymer-soluble finely divided particles,(2) the CT complex is formed either by at least one weaklypolymer-soluble electron donor and at least one polymer-soluble electronacceptor or by at least one weakly polymer-soluble electron acceptor andat least one polymer-soluble electron donor, and (3) microcrystallineneedles grow from the weakly polymer-soluble particles in the polymermass, which microcrystalline needles are in contact with and connect theweakly polymer-soluble particles to form a network which penetrates thepolymer mass;wherein said electron acceptor is at least onetetracyanoethylene or tetracyanoquinodimethane of formula X, or at leastone N,N'-dicyanoquinodimethane of formula XI, or a mixture thereof##STR39## wherein R₁₆, R₁₇, R₁₈ and R₁₉ are each independently of oneanother C₁ -C₁₂ -alkyl, C₁ -C₁₂ -alkoxy, C₁ -C₁₂ -alkylsulfido, phenyl,halogen, --CN or H, R₁₆ and R₁₇ are together a residue of ##STR40##--(CH₂)_(m) --, --(CH₂)_(m) --O--(CH₂)_(m) -- or --O--(CH₂)_(m) --O--, mis an integer 1-12 and R₁₈ and R₁₉ are each independently of the otherC₁ -C₁₂ -alkyl, C₁ -C₁₂ -alkoxy, C₁ -C₁₂ -alkylsulfido, phenyl, halogen,--CN or H, or R₁₆ and R₁₇ are each independently of the other C₁ -C₁₂-alkyl, C₁ -C₁₂ -alkoxy, C₁ -C₁₂ -alkylsulfido, phenyl, halogen, --CN orH and R₁₈ and R₁₉ are together a residue of ##STR41## --(CH₂)_(m) --,--(CH₂)_(m) --O--(CH₂)_(m) -- or --O--(CH₂)_(m) --O--, m is an integer1-12, in which the condensed aromatic rings may be substituted by one ortwo chlorine or bromine atoms or C₁ -C₄ -alkoxy and/or C₁ -C₄ -alkylgroups.
 20. A composition comprising a matrix of a thermoplastic,thermosetting or a structurally crosslinked polymer, in which isincorporated an electroconductive network of crystal needles of a chargetransfer complex (abbreviated to CT complex) from an electron donor andan electron acceptor, characterized in that(1) the matrix containsuniformly distributed an excess, with respect to the CT complexformation, either of at least one electron donor or at least oneelectron acceptor as weakly polymer-soluble finely divided particles,(2) the CT complex is formed either by at least one weaklypolymer-soluble electron donor and at least one polymer-soluble electronacceptor or by at least one weakly polymer-soluble electron acceptor andat least one polymer-soluble electron donor, and (3) microcrystallineneedles grow from the weakly polymer-soluble particles in the polymermass, which microcrystalline needles are in contact with and connect theweakly polymer-soluble particles to form a network which penetrates thepolymer mass;wherein said electron acceptor is at least one metalcomplex of formula XII ##STR42## wherein Me is Pt or Pd, and R₂₀ is--CN, --CH₃ or --CF₃.
 21. A composition comprising a matrix of athermoplastic, thermosetting or a structurally crosslinked polymer, inwhich is incorporated an electroconductive network of crystal needles ofa charge transfer complex (abbreviated to CT complex) from an electrondonor and an electron acceptor, characterized in that(1) the matrixcontains uniformly distributed an excess, with respect to the CT complexformation, either of at least one electron donor or at least oneelectron acceptor as weakly polymer-soluble finely divided particles,(2) the CT complex is formed either by at least one weaklypolymer-soluble electron donor and at least one polymer-soluble electronacceptor or by at least one weakly polymer-soluble electron acceptor andat least one polymer-soluble electron donor, and (3) microcrystallineneedles grow from the weakly polymer-soluble particles in the polymermass, which microcrystalline needles are in contact with and connect theweakly polymer-soluble particles to form a network which penetrates thepolymer mass;wherein said electron acceptor is a quinone.
 22. Acomposition according to claim 1, wherein said CT complex is representedby general formula XIII

    (D)(A).sub.n                                               (XIII),

wherein D is an electron donor, A is an electron acceptor and n is anumber 0.1-2.0, and the electron donor is weakly polymer-soluble if theelectron acceptor is polymer-soluble while the electron donor ispolymer-soluble if the electron acceptor is weakly polymer-soluble. 23.A composition according to claim 22, wherein the electron donor D isselected from 5,6,11,12-tetrathiotetracene,5,6,11,12-tetraselenotetracene, 2-fluoro- or2,3-difluoro-5,6,11,12-tetraselenotetracene,2,3,8,9-tetramethyl-5,6,11,12-tetrathiotetracene,2,3,8,9-tetramethyl-5,6,11,12-tetraselenotetracene,2-methyl-5,6,11,12-tetrathiotetracene,2,3,8,9-tetrafluoro-5,6,11,12-tetrathiotetracene,2,3,8,9-tetrafluoro-5,6,11,12-tetraselenotetracene,2,3-dichloro-5,6,11,12-tetraselenotetracene,2-fluoro-5,6,11,12-tetratellurotetracene,2,3,6,7-tetrathiophenyl-1,4,5,8-tetrathionaphthalene,2,3,6,7-tetramethoxyphenyl-1,4,5,8-tetrathionaphthalene,2,3,6,7-tetra-4-pyridylthio-1,4,5,8-tetrathionaphthalene,2,3,6,7-tetraphenylthio-1,4,5,8-tetraselenonaphthalene, or the compound##STR43##
 24. A composition according to claim 22, wherein the electrondonor D is 5,6,11,12-tetrathiotetracene or5,6,11,12-tetraselenotetracene.
 25. A composition according to claim 9,wherein said electron donor is at least one compound of formula I or Iaor a mixture thereof ##STR44## wherein X₁ is S, Se or Te, R₁, R₂, R₃ andR₄ are each independently of one another H or Cl, or R₁ and R₂ as wellas R₃ and R₄ are each ##STR45## or R₁, R₂, R₃ and R₄ are eachindependently of one another phenylthio, 4-methyl- or4-methoxyphenylthio or 4-pyridylthio, R₅, R₆, R₇ and R₈ are eachindependently of the other H or F, R₅ is CH₃ and R₆, R₇ and R₈ are H orR₅, R₆, R₇ and R₈ are CH₃, R₅ and R₆ are CH₃ or Cl and R₇ and R₈ are Hor R₅ and R₆ are H, R₇ is --COR₉ and R₈ is H or --COR₉, or R₅ and R₆ areH and R₇ and R₈ together are --CO--O--CO or --CO--NR₁₀ --CO--, R₉ ishalogen, --OH, --NH₂, or the residue of an alcohol or of primary orsecondary amine, or --OM, M being a cation and R₁₀ stands for H or theresidue of a primary amine which is diminished by an NH₂ -- group.
 26. Acomposition according to claim 9, wherein said electron donor is atleast one compound represented by formula II ##STR46## wherein R₁₁, R₁₂,R₁₃ and R₁₄ are each independently of one another C₁ -C₁₂ -alkyl,phenyl, C₁ -C₁₂ -alkylphenyl, C₁ -C₁₂ -alkoxyphenyl or H, or R₁₁ and R₁₂together are a residue of ##STR47## --(CH₂)_(p) --, --C(CH₃)₂--(CH₂)_(p) --C(CH₃)₂ -- or --S--(CH₂)_(p) --S--, p is an integer 1-12and R₁₃ and R₁₄ are each independently of the other C₁ C₁₂ -alkyl,phenyl, C₁ -C₁₂ -alkylphenyl, C₁ -C₁₂ -alkoxyphenyl or H, or R₁₁ and R₁₂are each independently of the other C₁ -C₁₂ -alkyl, phenyl, C₁ -C₁₂-alkylphenyl, C₁ -C₁₂ -alkoxyphenyl or H or R₁₃ and R₁₄ together are aresidue of ##STR48## --(CH₂)_(p) --, --C(CH₃)₂ --(CH₂)_(p) --C(CH₃)₂ --or --S--(CH₂)_(p) --S--, p is an integer 1-12, and X₂, X₃, X₄ and X₅ areSe or S.
 27. A composition according to claim 9, wherein said electrondonor is at least one compound of formula III ##STR49## wherein X₆ is S,Se or N--C₁ -C₁₂ -alkyl and R₁₅ is H, C₁ -C₁₂ -alkyl or substituted orunsubstituted phenyl.
 28. A composition according to claim 9, whereinsaid CT complex is represented by general formula XIII

    (D)(A).sub.n                                               (XIII),

wherein D is an electron donor, A is an electron acceptor and n is anumber 0.1-2.0, and the electron donor is weakly polymer-soluble if theelectron acceptor is polymer-soluble while the electron donor ispolymer-soluble if the electron acceptor is weakly polymer-soluble. 29.A composition according to claim 9, wherein said electron donor is atleast one compound of formula I or Ia or a mixture thereof ##STR50##wherein X₁ is S, Se or Te, R₁, R₂, R₃ and R₄ are each independently ofone another H or Cl, or R₁ and R₂ as well as R₃ and R₄ are each##STR51## or R₁, R₂, R₃ and R₄ are each independently of one anotherphenylthio, 4-methyl- or 4-methoxyphenylthio or 4-pyridylthio, R₅, R₆,R₇ and R₈ are each independently of the other H or F, R₅ is CH₃ and R₆,R₇ and R₈ are H or R₅, R₆, R₇ and R₈ are CH₃, R₅ and R₆ are CH₃ or Cland R₇ and R₈ are H or R₅ and R₆ are H, R₇ is --COR₉ and R₈ is H or--COR₉, or R₅ and R₆ are H and R₇ and R₈ together are --CO--O--CO or--CO--NR₁₀ --CO--, R₉ is halogen, --OH, --NH₂, or the residue of analcohol or of primary or secondary amine, or --OM, M being a cation andR₁₀ stands for H or the residue of a primary amine which is diminishedby an NH₂ -- group.
 30. A composition according to claim 17, whereinsaid electron donor is at least one compound represented by formula II##STR52## wherein R₁₁, R₁₂, R₁₃ and R₁₄ are each independently of oneanother C₁ -C₁₂ -alkyl, phenyl, C₁ -C₁₂ -alkylphenyl, C₁ -C₁₂-alkoxyphenyl or especially H, or R₁₁ and R₁₂ together are a residue of##STR53## --(CH₂)_(p) --, --C(CH₃)₂ --(CH₂)_(p) --C(CH₃)₂ -- or--S--(CH₂)_(p) --S--, p is an integer 1-12 and R₁₃ and R₁₄ are eachindependently of the other C₁ -C₁₂ -alkyl, phenyl, C₁ -C₁₂ -alkylphenyl,C₁ -C₁₂ -alkoxyphenyl or H, or R₁₁ and R₁₂ are each independently of theother C₁ -C₁₂ -alkyl, phenyl, C₁ -C₁₂ -alkylphenyl, C₁ -C₁₂-alkoxyphenyl or H or R₁₃ and R₁₄ together are a residue of ##STR54##--(CH₂)_(p) --, --C(CH₃)₂ --(CH₂)_(p) --C(CH₃)₂ -- or --S--(CH₂)_(p)--S--, p is an integer 1-12, and X₂, X₃, X₄ and X₅ are Se or S.
 31. Acomposition according to claim 17, wherein said electron donor is atleast one compound of formula III ##STR55## wherein X₆ is S, Se or N--C₁-C₁₂ -alkyl and R₁₅ is H, C₁ -C₁₂ -alkyl or substituted or unsubstitutedphenyl.
 32. A composition according to claim 17, wherein said CT complexis represented by general formula XIII

    (D)(A).sub.n                                               (XIII),

wherein D is an electron donor, A is an electron acceptor and n is anumber 0.1-2.0, and the electron donor is weakly polymer-soluble if theelectron acceptor is polymer-soluble while the electron donor ispolymer-soluble if the electron acceptor is weakly polymer-soluble. 33.A composition according to claim 18, wherein said electron donor is atleast one compound of formula I or Ia or a mixture thereof ##STR56##wherein X₁ is S, Se or Te, R₁, R₂, R₃ and R₄ are each independently ofone another H or Cl, or R₁ and R₂ as well as R₃ and R₄ are each##STR57## or R₁, R₂, R₃ and R₄ are each independently of one anotherphenylthio, 4-methyl- or 4-methoxyphenylthio or 4-pyridylthio, R₅, R₆,R₇ and R₈ are each independently of the other H or F, R₅ is CH₃ and R₆,R₇ and R₈ are H or R₅, R₆, R₇ and R₈ are CH₃, R₅ and R₆ are CH₃ or Cland R₇ and R₈ are H or R₅ and R₆ are H, R₇ is --COR₉ and R₈ is H or--COR₉, or R₅ and R₆ are H and R₇ and R₈ together are --CO--O--CO or--CO--NR₁₀ --CO--, R₉ is halogen, --OH, --NH₂, or the residue of analcohol or of primary or secondary amine, or --OM, M being a cation andR₁₀ stands for H or the residue of a primary amine which is diminishedby an NH₂ -- group.
 34. A composition according to claim 18, whereinsaid electron donor is at least one compound represented by formula II##STR58## wherein R₁₁, R₁₂, R₁₃ and R₁₄ are each independently of oneanother C₁ -C₁₂ -alkyl, phenyl, C₁ -C₁₂ -alkylphenyl, C₁ -C₁₂-alkoxyphenyl or especially H, or R₁₁ and R₁₂ together are a residue##STR59## --(CH₂)_(p) --, --C(CH₃)₂ --(CH₂)_(p) --C(CH₃)₂ -- or--S--(CH₂)_(p) --S--, p is an integer 1-12 and R₁₃ and R₁₄ are eachindependently of the other C₁ -C₁₂ -alkyl, phenyl, C₁ -C₁₂ -alkylphenyl,C₁ -C₁₂ -alkoxyphenyl or H, or R₁₁ and R₁₂ are each independently of theother C₁ -C₁₂ -alkyl, phenyl, C₁ -C₁₂ -alkylphenyl, C₁ -C₁₂-alkoxyphenyl or H or R₁₃ and R₁₄ together are a residue of ##STR60##--(CH₂)_(p) --, --C(CH₃)₂ --(CH₂)_(p) --C(CH₃)₂ -- or --S--(CH₂)_(p)--S--, p is an integer 1-12, and X₂, X₃, X₄ and X₅ are Se or S.
 35. Acomposition according to claim 18, wherein said electron donor is atleast one compound of formula III ##STR61## wherein X₆ is S, Se or N--C₁-C₁₂ -alkyl and R₁₅ is H, C₁ -C₁₂ -alkyl or substituted or unsubstitutedphenyl.
 36. A composition according to claim 18, wherein said CT complexis represented by general formula XIII

    (D)(A).sub.n                                               (XIII),

wherein D is an electron donor, A is an electron acceptor and n is anumber 0.1-2.0, and the electron donor is weakly polymer-soluble if theelectron acceptor is polymer-soluble while the electron donor ispolymer-soluble if the electron acceptor is weakly polymer-soluble. 37.A composition according to claim 19, wherein said electron donor is atleast one compound of formula I or Ia or a mixture thereof ##STR62##wherein X₁ is S, Se or Te, R₁, R₂, R₃ and R₄ are each independently ofone another H or Cl, or R₁ and R₂ as well as R₃ and R₄ are each##STR63## or R₁, R₂, R₃ and R₄ are each independently of one anotherphenylthio, 4-methyl- or 4-methoxyphenylthio or 4-pyridylthio, R₅, R₆,R₇ and R₈ are each independently of the other H or F, R₅ is CH₃ and R₆,R₇ and R₈ are H or R₅, R₆, R₇ and R₈ are CH₃, R₅ and R₆ are CH₃ or Cland R₇ and R₈ are H or R₅ and R₆ are H, R₇ is --COR₉ and R₈ is H or--COR₉, or R₅ and R₆ are H and R₇ and R₈ together are --CO--O--CO or--CO--NR₁₀ --CO--, R₉ is halogen, --OH, --NH₂, or the residue of analcohol or of primary or secondary amine, or --OM, M being a cation andR₁₀ stands for H or the residue of a primary amine which is diminishedby an NH₂ -- group.
 38. A composition according to claim 19, whereinsaid electron donor is at least one compound represented by formula II##STR64## wherein R₁₁, R₁₂, R₁₃ and R₁₄ are each independently of oneanother C₁ -C₁₂ -alkyl, phenyl, C₁ -C₁₂ -alkylphenyl, C₁ -C₁₂-alkoxyphenyl or H, or R₁₁ and R₁₂ together are a residue of ##STR65##--(CH₂)_(p) --, --C(CH₃)₂ --(CH₂)_(p) --C(CH₃)₂ -- or --S--(CH₂)_(p)--S--, p is an integer 1-12 and R₁₃ and R₁₄ are each independently ofthe other C₁ -C₁₂ -alkyl, phenyl, C₁ -C₁₂ -alkylphenyl, C₁ -C₁₂-alkoxyphenyl or H, or R₁₁ and R₁₂ are each independently of the otherC₁ -C₁₂ -alkyl, phenyl, C₁ -C₁₂ -alkylphenyl, C₁ -C₁₂ -alkoxyphenyl or Hor R₁₃ and R₁₄ together are a residue of ##STR66## --(CH₂)_(p) --,--C(CH₃)₂ --(CH₂)_(p) --C(CH₃)₂ -- or --S--(CH₂)_(p) --S--, p is aninteger 1-12, and X₂, X₃, X₄ and X₅ are Se or S.
 39. A compositionaccording to claim 19, wherein said electron donor is at least onecompound of formula III ##STR67## wherein X₆ is S, Se or N--C₁ -C₁₂-alkyl and R₁₅ is H, C₁ -C₁₂ -alkyl or substituted or unsubstitutedphenyl.
 40. A composition according to claim 19, wherein said CT complexis represented by general formula XIII

    (D)(A).sub.n                                               (XIII),

wherein D is an electron donor, A is an electron acceptor and n is anumber 0.1-2.0, and the electron donor is weakly polymer-soluble if theelectron acceptor is polymer-soluble while the electron donor ispolymer-soluble if the electron acceptor is weakly polymer-soluble. 41.A composition according to claim 20, wherein said electron donor is atleast one compound of formula I or Ia or a mixture thereof ##STR68##wherein X₁ is S, Se or Te, R₁, R₂, R₃ and R₄ are each independently ofone another H or Cl, or R₁ and R₂ as well as R₃ and R₄ are each##STR69## or R₁, R₂, R₃ and R₄ are each independently of one anotherphenylthio, 4-methyl- or 4-methoxyphenylthio or 4-pyridylthio, R₅, R₆,R₇ and R₈ are each independently of the other H or F, R₅ is CH₃ and R₆,R₇ and R₈ are H or R₅, R₆, R₇ and R₈ are CH₃, R₅ and R₆ are CH₃ or Cland R₇ and R₈ are H or R₅ and R₆ are H, R₇ is --COR₉ and R₈ is H or--COR₉, or R₅ and R₆ are H and R₇ and R₈ together are --CO--O--CO or--CO--NR₁₀ --CO--, R₉ is halogen, --OH, --NH₂, or the residue of analcohol or of primary or secondary amine, or --OM, M being a cation andR₁₀ stands for H or the residue of a primary amine which is diminishedby an NH₂ -- group.
 42. A composition according to claim 20, whereinsaid electron donor is at least one compound represented by formula III##STR70## wherein R₁₁, R₁₂, R₁₃ and R₁₄ are each independently of oneanother C₁ -C₁₂ -alkyl, phenyl, C₁ -C₁₂ -alkylphenyl, C₁ -C₁₂-alkoxyphenyl or especially H, or R₁₁ and R₁₂ together are a residue of##STR71## --(CH₂)_(p) --, --C(CH₃)₂ --(CH₂)_(p) --C(CH₃)₂ -- or--S--(CH₂)_(p) --S--, p is an integer 1-12 and R₁₃ and R₁₄ are eachindependently of the other C₁ -C₁₂ -alkyl, phenyl, C₁ -C₁₂ -alkylphenyl,C₁ -C₁₂ -alkoxyphenyl or especially H, or R₁₁ and R₁₂ are eachindependently of the other C₁ -C₁₂ -alkyl, phenyl, C₁ -C₁₂ -alkylphenyl,C₁ -C₁₂ -alkoxyphenyl or H or R₁₃ and R₁₄ together are a residue of##STR72## --(CH₂)_(p) --, --C(CH₃)₂ --(CH₂)_(p) --C(CH₃)₂ -- or--S--(CH₂)_(p) --S--, p is an integer 1-12, and X₂, X₃, X₄ and X₅ are Seor S.
 43. A composition according to claim 20, wherein said electrondonor is at least one compound of formula III ##STR73## wherein X₆ is S,Se or N--C₁ -C₁₂ -alkyl and R₁₅ is H, C₁ -C₁₂ -alkyl or substituted orunsubstituted phenyl.
 44. A composition according to claim 20, whereinsaid CT complex is represented by general formula XIII

    (D)(A).sub.n                                               (XIII),

wherein D is an electron donor, A is an electron acceptor and n is anumber 0.1-2.0, and the electron donor is weakly polymer-soluble if theelectron acceptor is polymer-soluble while the electron donor ispolymer-soluble if the electron acceptor is weakly polymer-soluble. 45.A composition according to claim 21, wherein said electron donor is atleast one compound of formula I or Ia or a mixture thereof ##STR74##wherein X₁ is S, Se or Te, R₁, R₂, R₃ and R₄ are each independently ofone another H or Cl, or R₁ and R₂ as well as R₃ and R₄ are each##STR75## or R₁, R₂, R₃ and R₄ are each independently of one anotherphenylthio, 4-methyl- or 4-methoxyphenylthio or 4-pyridylthio, R₅, R₆,R₇ and R₈ are each independently of the other H or F, R₅ is CH₃ and R₆,R₇ and R₈ are H or R₅, R₆, R₇ and R₈ are CH₃, R₅ and R₆ are CH₃ or Cland R₇ and R₈ are H or R₅ and R₆ are H, R₇ is --COR₉ and R₈ is H or--COR₉, or R₅ and R₆ are H and R₇ and R₈ together are --CO--O--CO or--CO--NR₁₀ --CO--, R₉ is halogen, --OH, --NH₂, or the residue of analcohol or of primary or secondary amine, or --OM, M being a cation andR₁₀ stands for H or the residue of a primary amine which is diminishedby an NH₂ -- group.
 46. A composition according to claim 21, whereinsaid electron donor is at least one compound represented by formula II##STR76## wherein R₁₁, R₁₂, R₁₃ and R₁₄ are each independently of oneanother C₁ -C₁₂ -alkyl, phenyl, C₁ -C₁₂ -alkylphenyl, C₁ -C₁₂-alkoxyphenyl or H, or R₁₁ and R₁₂ together are a residue of ##STR77##--(CH₂)_(p) --, --C(CH₃)₂ --(CH₂)_(p) --C(CH₃)₂ -- or --S--(CH₂)_(p)--S--, p is an integer 1-12 and R₁₃ and R₁₄ are each independently ofthe other C₁ -C₁₂ -alkyl, phenyl, C₁ -C₁₂ -alkylphenyl, C₁ -C₁₂-alkoxyphenyl or H, or R₁₁ and R₁₂ are each independently of the otherC₁ -C₁₂ -alkyl, phenyl, C₁ -C₁₂ -alkylphenyl, C₁ -C₁₂ -alkoxyphenyl or Hor R₁₃ and R₁₄ together are a residue of ##STR78## --(CH₂)_(p) --,--C(CH₃)₂ --(CH₂)_(p) --C(CH₃)₂ -- or --S--(CH₂)_(p) --S--, p is aninteger 1-12, and X₂, X₃, X₄ and X₅ are Se or S.
 47. A compositionaccording to claim 21, wherein said electron donor is at least onecompound of formula III ##STR79## wherein X₆ is S, Se or N--C₁ -C₁₂-alkyl and R₁₅ is H, C₁ -C₁₂ -alkyl or substituted or unsubstitutedphenyl.
 48. A composition according to claim 21, wherein said CT complexis represented by general formula XIII

    (D)(A).sub.n                                               (XIII),

wherein D is an electron donor, A is an electron acceptor and n is anumber 0.1-2.0, and the electron donor is weakly polymer-soluble if theelectron acceptor is polymer-soluble while the electron donor ispolymer-soluble if the electron acceptor is weakly polymer-soluble.